Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
  • C10M125/24—Compounds containing phosphorus, arsenic or antimony
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
  • C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/085—Phosphorus oxides, acids or salts
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
  • C10M2201/18—Ammonia
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
  • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2010/00—Metal present as such or in compounds
  • C10N2010/02—Groups 1 or 11

Definitions

• the present invention relates generally to the field of metal conversion surfaces, in particular, the creation of a phosphate-metal chemisorbed layer for iron and aluminum parts as well as to other metal substrates capable of forming a conversion surface.
• the creation of an iron-phosphate conversion surface is known to create a surface that exhibits high dry lubricity, among other benefits.
• Creation of the iron- phosphate conversion surface on an iron part or piece of equipment traditionally is accomplished through a phosphatizing bath process.
• This bath also typically includes the element of zinc in order to optimize the process of deposition of the phosphate onto the surface of the item of interest. While the use of a bath process is practical for coating particular types of parts or pieces, i.e. large items where the surface is otherwise exposed to the elements, the bath process requires that the parts to be treated be disassembled in order to receive the coating.
• U.S. Patent No. 5,540,788 issued to DeFalco teaches a process for creating an iron-phosphorus surface through the formation of a conversion surface on iron substrates by delivering the phosphatizing compound in a lubricating fluid.
• This method includes the formation of a conversion surface to create the iron/phosphate surface onto completed machinery engines.
• the composition can be introduced through the lubricating oil into a running engine.
• the composition disclosed includes a source of phosphoric acid, an alkali metal hydroxide and a source of reactive NH2 groups.
• the source of the reactive NH2 groups produces the reactive NH2 groups as a result of the highly exothermic reaction that is described.
• the reactive NH2 groups produced in the DeFalco patent are best described as phosphamids. This specific chemistry results from the highly exothermic reaction described in the DeFalco patent. It is also noted that the physical conditions of having a high pH results in the production of free ammonia. When the phosphamids circulate with the lubrication medium in the engine, a phosphate-iron conversion surface specific to this composition was created.
• Aluminum alloy engines include a lubricating oil for lubricity of the engine.
• the lubricating oil is selected for high film strength to minimize wear. This prevents metal-to-metal contact and provides protection against piston scuffing.
• two-cycle motors lose power and torque.
• the aluminum pistons expand from heat and cause an increase in friction.
• Various proprietary lubricating oils have been introduced into the market place to improve performance at high operating temperatures.
• the ASTM D-4863 two-cycle motor lubricity test measures torque output at 350 °C (662 °F) and is a benchmark for performance.
• No. 6,172,013 discloses lubricating oil compositions having enhanced friction coefficient and wear properties through the use of additives of molybdenum and diesters of aliphatic or aromatic dicarboxylic acids. Adducts of glyoxylic acids and phenols are known.
• U.S. Pat. No. 5,281,346, Adams discloses a two- cycle engine lubricant comprising, alkali or alkaline earth metal salts of carboxylic aromatic acids.
• the present invention includes compositions and methods useful for the creation of phosphorus-containing conversion surfaces on metal components.
• the composition of the invention is useful to create a thin layer on metal surfaces.
• the invention includes a phosphorus-containing solution containing [Y]H 2 PO 4 , [Y] 2 HPO 4 , and water or other solvent as components of an intermediate solution, where Y is a cation.
• [Y]H 2 PO 4 , [Y] 2 HPO 4 as well as other salts discussed herein are also called salt components.
• the cationic portion of the salt components can be any cation, with potassium being a preferred cation. In this case, the preferred components would be KH 2 PO 4 , K 2 HPO 4 , and water.
• the intermediate solution is mixed with a carrier fluid.
• the carrier fluid is any fluid that is operable to maintain the salts in at least a partially dispersed state within the carrier fluid.
• the resulting phosphorus- containing solution is operable to create a phosphate-metal layer on a metal substrate when the phosphorus-containing solution is placed in contact with the metal substrate.
• a group of preferred cations for the salts are the alkali metals or Group 1 A elements. While orthophosphoric acids have been described, the invention also includes pyrophosphoric acids, which are the condensed analogs and therefore derivatives of and equivalent to orthophosphoric acid. It is noted that, through the process to condense the orthophosphoric acid to pyrophosphoric acids, the PO 4 3" become P 2 O 7 " or other condensed phosphates. Therefore, [Y]H 2 PO 4 , [Y] 2 HPO 4 and [NH 4 ] HPO 4 are precursors to pyrophosphoric acids. The use of the pyrophosphoric form is therefore encompassed within the definition of the orthophosphate form, which can be expressed as [Y]H 2 PO 4 , [Y] HPO 4 and [NH 4 ] HPO 4 and in similar form.
• the phosphorus-containing solution is essentially free of zinc. While some amount of zinc can exist in the solution, for example, when it is present in raw materials, zinc is not added or present in a quantity beneficial for plating. Thus, the phosphorus-containing solution is considered essentially free of zinc. Beneficially, the solution is also substantially free of halogens.
• Another preferred embodiment of the phosphorus-containing solution includes the addition of [NR 4 ] 2 HPO 4 to the intermediate solution of [Y]H 2 PO 4 , [Y] 2 HPO 4 , and water or other solvent.
• R in [NR 4 ] can be an alkyl group, hydrogen, or combinations of both. Thus, this encompasses ammonium as well as amine phosphates.
• the nitrogen in the solution is essentially all in the form of ammonium or amine ions. There is at most a negligible amount of free ammonia such that the solution is substantially ammonia free.
• Yet another embodiment includes the addition of [X]C H 3 O 2 where C 2 H 3 O 2 " ion is an acetate group such that the intermediate solution contains at least [Y]H 2 PO 4 , [Y] 2 HPO 4 , [XJC2H3O2 and water or other solvent.
• Preferred embodiments include X as NH or K or other Group IA elements.
• [NR ] 2 HPO where R hydrogen, alkyl groups or a combination of both, can also be added to this mixture. This intermediate solution is combined with the carrier fluid and the water or other solvent is largely removed to create the phosphorus-containing solution.
• the solvent such as alcohols
• the solvent have sufficient volatility to allow for removal from the intermediate solution mixed with carrier fluid through the addition of heat, although this is not a required characteristic.
• the phosphorus-containing solution is prepared using ammonium compounds, ammonium compounds being defined as those compounds containing NHx groups, the nitrogen in the phosphorus-containing solution is essentially all in the form of ammonium ions. Amine ions are also encompassed herein. There is at most a negligible amount of free ammonia.
• the mixture is advantageously created without the production of excessive amounts of heat, i.e., no highly exothermic reaction is performed.
• the phosphorous-containing solution has a pH between about 6.0 and 8.0.
• the phosphorus-containing solution of the invention can be used in various types of environments, such as aqueous or hydrophilic environments, i the case of a hydrophilic environment, it is advantageous to include a carrier fluid and a dispersant to promote dispersion in the carrier fluid.
• the carrier fluid can be a lubricating fluid that is to be placed in contact with the metal parts or metal substrate or, in a preferred embodiment, the carrier fluid is a separate hydrophilic fluid that is highly miscible with lubricating fluid, such as a motor oil.
• One characteristic of the carrier fluid is that the salts of the phosphorus-containing solution are at least partially soluble in the carrier fluid.
• the carrier fluid is a quantity of a target fluid, such as the lubricating fluid.
• the target fluid is the fluid that is identified as the majority fluid that is intended to bring the phosphorus-containing solution into contact with the metal to be treated.
• the phosphorus-containing solution can be dispersed through the target fluid through the use of physical mixing, such as a high speed shear mixer, or other means. In such instances, the target fluid acts as the carrier fluid.
• the current invention includes a process for creating a conversion surface on a metal part or metal substrate in a system using the phosphorus-containing solution.
• the system can be as simple as a metal part operable to be brought into contact with the phosphorus-containing solution or it can be a complex series of parts, such as in an engine, where the phosphorus-containing solution is brought into contact with at least part of the system.
• the part is at least partially in contact with the phosphorus-containing solution or target fluid containing the phosphorus-containing solution
• the phosphate-metal layer surface is created resulting in a converted metal substrate have the phosphate-metal layer or conversion surface on surfaces of the metal substrate contacted by the phosphorus-containing solution.
• the amount of phosphorus-containing solution used is the amount effective to create the conversion surface.
• Preferred embodiments of the target fluid that is contacting the part include a lubricating fluid or a phosphating bath.
• the conversion surface that is created as a result of this process has characteristics and composition specific to the metal contained in the metal part and to the phosphorus-containing solution.
• the metal part includes iron
• a phosphate-iron surface is created on the surface of the iron.
• the metal part includes aluminum
• an aluminum-phosphate surface is created.
• the metal contains nickel
• a phosphate-nickel surface is created. Similar results are observed with chromium and molybdenum.
• the present invention includes compositions and methods useful for the creation of phosphorus-containing conversion surfaces on non-ferrous components, such as aluminum two cycle engines.
• the composition of the invention is useful to create a thin layer on metal surfaces.
• One preferred embodiment includes a lubricating composition or lubricant that has a substantial amount of an oil having a lubricating viscosity. An amount of the phosphorus-containing solution is added to the oil thereby creating a lubricating composition operable to create a conversion surface upon a metal component upon being brought into contact with the metal component.
• Another embodiment of the invention includes a method of forming a non- ferrous metal-phosphate conversion surface on non-ferrous metal components by contacting the non-ferrous metal component in a contact region with an active phosphorus solution to form the non-ferrous metal-phosphate conversion surface on the contact region.
• the contact region can be limited to a portion of the surface of the metal component or can encompass the entire metal component.
• the active phosphorus solution is prepared by mixing a phosphorus-containing acid with an alkali metal hydroxide salt and an ammonium/amine compound under conditions designed to create a highly exothermic reaction thereby producing the active phosphorus-solution.
• the ammonium/amine compound is an active compound that contains either ammonium or amine and is operable to interact in the exothermic reaction. Ammonium hydroxide and ammonia paratungstate are two examples of such compounds.
• the active phosphorus solution was disclosed as being useful to produce conversion surfaces on iron, new investigations indicate that, when carried to the surface of aluminum in an appropriate carrier, the active phosphorus solution can be used to create a conversion surface on aluminum.
• Aluminum-phosphate conversion surfaces are created upon contacting of the aluminum part or engine with the phosphorus-containing solution of the invention or the active phosphorus solution. With either solution, this conversion surface can be produced in bath processes or in situ. Unlike traditional electro-deposition in baths, the phosphorus-containing solution of the current invention does not utilize zinc.
• the phosphorus-containing solution can be delivered into contact to create the aluminum conversion surface on the aluminum part through the use of a target fluid.
• a target fluid is a lubricating oil in a two-cycle aluminum engine as part of a motorized vehicle or other equipment.
• the phosphorus-containing solution is combined with the lubricating oil to create a lubricating composition.
• the lubricating composition including the substantial amount of oil having a lubricating viscosity and an amount of the phosphorus-containing primary solution operable to create a conversion surface upon the aluminum part or metal component.
• the active phosphorus solution is also useful for creating the conversion surface on an aluminum part by contacting the active phosphorus solution to the aluminum engine, preferably delivered into contact through the use of target fluid.
• amounts used in testing include amounts between about .01% by weight to about .5% by weight of phosphorus in the lubricating composition.
• a preferred embodiment includes .3% by weight of phosphorus, hicreased amounts of phosphorus are effective as well. It is notable that a very cost-effective solution can be prepared with low weight percent of phosphorus.
• the process of the invention includes the creation of conversion surfaces using the phosphorus-containing solution of the invention on any metal part or metal substrate.
• metal part or metal substrate For example, aircraft parts are often made of aluminum. The application of the conversion surface upon aircraft parts can reduce coefficients of friction. Motorboat engines, lawn mowers or other equipment that includes metal motors or metal parts benefit from the conversion surface of the invention. By creating a cost-effective manner of creating the conversion surface, application to a wide range of equipment becomes economically feasible. This process is also used with the active phosphorus solution on non-ferrous components.
• the conversion surface is formed as a result of contacting the aluminum alloy of the part or component with an amount of the phosphorus-containing solution or active phosphorus solution operable to create the conversion surface.
• the resulting conversion surface with use of the phosphorus-containing solution includes aluminum phosphate and aluminum oxide.
• the addition of the phosphorus-containing solution to an aluminum surface results in the formation of the reaction product of AlPO 4 , aluminum phosphate, and Al O 3 , aluminum oxide, as a conversion surface on the aluminum component. Test run using infrared and X-ray testing techniques confirm the existence of these species.
• Other aluminum species also are produced depending upon composition of an aluminum alloy of the aluminum surface and side reactions. In a preferred embodiment, acetate compounds are utilized to manipulate the pH of the solution.
• One example of a preferred formulation includes the phosphorus-containing solution with the following amounts
• the identified salts are mixed with and dissolved in an amount of water sufficient to at least partially dissolve the salts.
• the test shown above used 55.6 moles of water. This creates the intermediate solution, which in this case has 2.9 mole % of KH 2 PO 4 , 1.2 mole % of K 2 HPO 4 , 0.5 mol % of K 2 HPO 4 and 95.3 mol % of water.
• the intermediate solution is then mixed with the carrier fluid.
• the water is then driven off thermally from the mixture of the intermediate solution with the carrier fluid to produce the phosphorus-containing solution of the invention.
• the resulting phosphorus-containing solution of the invention is referred to as being substantially dry or water free due to the negligible amount of water remaining in the solution.
• the water is driven off to a level of around 0.1 wt% of the phosphorus-containing solution. It is noted that more water can remain in the solution without changing the functionality of the phosphorus-containing solution, but 0.1 wt % has been selected as a preferred product specification.
• Phosphorus-containing solutions with K or other cation between 0.16 and 16 mole % have been evaluated. Solutions outside of this range will also be effective, although with varying degrees of cost effectiveness or efficiency.
• the pH of the phosphorus-containing solution can be controlled through manipulation of the ratios of components. By manipulating the ratios of the resulting H PO 4" and HPO 4 2" ions, the phosphorus-containing solution can be created in the preferred pH range of about 6.0 to about 8.0. For example, the ratio is approximately 15.8 for a pH of 6. The ratio is about .0158 for a pH of 8. Test results were controlled for a pH of 7, although the entire range is considered neutral and therefore preferred. Through simulation, the following amounts are anticipated to reach the indicated pH using the ratio as the only means of manipulating the pH.
• Preparation of the formulation includes dissolving KH 2 PO , K 2 HPO and KAcetate salts in water. No ammonium salts are used in this example, so the final formulation will contain no ammonia.
• the procedure includes adding 51 lbs of deionized water, 17.6 lbs of KH 2 PO 4 , 14.2 lbs of K 2 HPO 4 and 2.2 lbs of Kacetate in that order to two 5-gallon plastic pails. An additional 16.4 lbs of water was added thereafter. The salts were added to the water with rapid mechanical agitation and the mixture was heated after the addition of all the salts. The dissolution of the KH 2 PO was slightly endothermic, dropping the temperature of the batch by 4 to 5 degrees C. While complete dissolution is not necessary, this experiment included heating the mixture to 40 degrees C in order to dissolve the remaining salts. Alternately, additional water can be added if complete dissolution is desired.
• the pH after complete dissolution was in the target range of 7.0 - 7.1 so no adjustment of pH, such as, through the addition of KOH or acetic acid, was made.
• the resulting P value was approximately 65,000 ppm after final dilution such that no salts crystallize out of solution.
• KH 2 PO 4 is between 38 and 55 mole percent of the salts.
• K 2 HPO 4 ranged from 24 to 35 mole percent of the salts.
• the salts were diluted with water such that moles of phosphorus (P) per liter of the intermediate solution was approximately 2.61 moles/L. This intermediate solution was mixed with the carrier fluid. Phosphorus-containing solutions prepared with much lower concentrations of phosphorus have also been found to be effective.
• [NH 4 ]C 2 H 3 O 2 can also be referred to as [NH 4 ]Oac.
• KH 2 PO 4 , K 2 HPO 4 , [NH 4 ] 2 HPO 4 and water are created into the intermediate solution that is added to refined oil carrier fluid and mixed with dispersants to create the phosphorus-containing solution.
• exemplary dispersants include alkenyl succinimides or similar type of dispersants, including the previously-marketed product TFA 4690C.
• a dispersant with a total base number of from 30 to 160 on an oil-free basis is used.
• the phosphorus-containing solution preferably ranges from approximately 8 to 12 wt % of the intermediate solution while the refined oil carrier fluid ranges from 88 to 92 wt % of the resulting mixture.
• the inte ⁇ nediate solution is added in at approximately 10 wt. % of the refined oil carrier fluid in a preferred embodiment.
• the resulting mixture is heated to drive off a significant amount of water.
• the resulting mixture exhibits characteristics that can be described as a colloid or an emulsion.
• an effective amount of the phosphorus in the phosphorus-containing solution can be very dilute and still remain effective.
• One example of a preferred embodiment is 0.3 wt% phosphorus in the intermediate solution.
• the phosphorus content can be in the range of 5 - 100 ppb and still be effective.
• Preferred range of phosphorus in the phosphorus-containing solution is 300-1250 ppm. Additional preferred range of phosphorus is 300-600 ppm. Particularly preferred range of phosphorus is 300-400 ppm. Higher amounts are also effective as shown in the previous examples.
• An example of an alternate embodiment of the phosphorus-containing solution includes mixing about 2.6 molar (M) orthophosphate with alkali metal and ammonium cations, having a pH of 7 at ambient temperatures. A measured volume of this aqueous phosphorus-containing solution is suspended in an oil-dispersant mixture, most of the water removed thermally, and diluted to about 0.3 wt% P.
• the phosphorus-containing solution can be contacted to metal parts while the engine is ninning and without disassembly of the engine.
• Scanning electron microscopy (SEM) of the steel surface after the application of the phosphorus-containing solution in the oil-based mixture shows a relatively smooth layer.
• SEM Scanning electron microscopy
• This layer is of variable composition and contains Fe, O, P, N, and K. The layer is believed to form from the reaction of phosphate species in the mixtures with the oxide surface of the metal (Fe), initially of about 25 Angstroms in thickness.
• the surface compounds resulting from this chemical reaction resulting in the conversion layer appear to range from the simple FePO 4 to more complex phosphates such as NH 4 Fe 2 [PO 4 ] 2 , K 3 Fe 3 [PO 4 ] 4 xH 2 O, NH 4 Fe 3 [H 2 PO 4 ] 6 [HPO 4 ] 2 xH 2 O, KFe 2 [HPO ] 2 [PO 4 ], and related compounds, depending upon operating conditions. Coordination of the phosphate structure to the surface metal (Fe) ions in the surface layer is believed to be the origin of the stability of these surface compounds.
• the diverse oils of lubricating viscosity include natural and synthetic lubricating oils and mixtures thereof.
• These lubricants include crankcase lubricating oils for spark-ignited and compression-ignited internal combustion engines, including automobile and truck engines, two-cycle engines, aviation piston engines, marine and railroad diesel engines, and the like. They can also be used in gas engines, stationary power engines and turbines and the like. Automatic transmission fluids, transaxle lubricants, gear lubricants, metal-working lubricants, hydraulic fluids and other lubricating oil and grease compositions can also benefit from the incorporation of the compositions of the present invention.
• the phosphamid mixture continues to be useful and is the subject of further development as disclosed herein.
• the exothermic reaction and the production of free ammonia at elevated pHs are two characteristics of phosphamid production that, under particular circumstances, can be considered less desirable.
• the phosphorus- containing solution of the current invention avoids the production of free ammonia and the related issues through maintaining pH in a range of approximately 6 to 8, or maintaining the pH below the level at which ammonia is formed, as well as avoiding the results and complexity of the creation of the highly exothermic reaction.
• Tests of the active phosphorus solution indicate that the active phosphorus solution interacts with non-ferrous metals to create conversion surfaces.
• An exemplary non-ferrous metal discussed above is aluminum.
• the active phosphorus solution creates a phosphorus-aluminum conversion surface when brought into contact with aluminum.
• Other non-ferrous metals capable of creating conversion surfaces also interact with the active phosphorus solution.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Lubricants (AREA)
• Chemical Treatment Of Metals (AREA)

Applications Claiming Priority (5)

Publications (1)

Family

ID=32853349

Family Applications (1)

Country Status (12)

Families Citing this family (9)

Family Cites Families (19)

• 2004
  • 2004-01-30 EP EP04707124A patent/EP1601814A2/en not_active Withdrawn
  • 2004-01-30 KR KR1020057014158A patent/KR100764271B1/ko not_active Expired - Fee Related
  • 2004-01-30 JP JP2006503240A patent/JP2006527301A/ja not_active Abandoned
  • 2004-01-30 AU AU2004209439A patent/AU2004209439B2/en not_active Ceased
  • 2004-01-30 CA CA002514795A patent/CA2514795A1/en not_active Abandoned
  • 2004-01-30 MX MXPA05008117A patent/MXPA05008117A/es unknown
  • 2004-01-30 EA EA200501211A patent/EA200501211A1/ru unknown
  • 2004-01-30 PL PL378289A patent/PL378289A1/pl unknown
  • 2004-01-30 BR BR0406703-7A patent/BRPI0406703A/pt not_active IP Right Cessation
  • 2004-01-30 WO PCT/US2004/002886 patent/WO2004070081A2/en not_active Ceased
  • 2004-01-30 US US10/768,613 patent/US20040182481A1/en not_active Abandoned
  • 2004-02-02 UY UY28176A patent/UY28176A1/es unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events