Patent Application
20080206874
The present invention relates to the analysis of the quality or identity of functional fluids. In particular, the invention relates to using an aerosol, mist, spray, liquid or semi liquid delivery system for the reagent solution containing the indicator or marker. This system comprises a reagent containing the indicator or marker that produces a color in the presence of reactants such as basic components. Oxidants, and/or wear metals in a functional fluid or that produces a color in the presence of a marker present in the functional fluid and a method to deliver the reagent solution.
Functional fluids are employed in a variety of automotive, off-highway vehicles, on-highway vehicles, equipment, machines, metal working and industrial applications. It is important to know the identity, quality and condition of such functional fluids to prevent the improper and ineffective utilization of the functional fluid. A quality functional fluid insures that the condition of the device/equipment containing the functional fluid is productive and properly functioning. It is, therefore, desirable to monitor the identity, and the physical and/or chemical conditions of functional fluids.
Methods exist for the analysis of functional fluids using various reagents in determining the presence and/or concentration of various constituents of the functional fluids. Specific reagents may be employed for determining the presence and concentration of components in functional fluids. These methods generally analyze for pH, coloring agents, and contaminants using reactive reagents on test strips. These methods generally require controlled conditions. Further, these methods may be subjective and inaccurate.
Other methods and apparatus for assessing the quality of a used fluid include placing a measured amount of fluid upon an absorbent material, heating the sample and awaiting dispersion of the sample. The amount of undispersed sample may then be measured and rated quantitatively. These methods and apparatus require significant controlled conditions, including measurement of the fluid sample volume, the use of a template to measure and rate the quantity of undispersed the sample. Additionally these methods can include heating of the sample, and awaiting dispersal of the sample. Another method to analyze oil is disclosed in U.S. Pat. No. 5,313,824; to Hergruth, et al. comprising the steps of obtaining a sample of the oil, placing the sample upon the medium, maintaining the medium in a desired position for an effective period of time for the spot to be visible, visually comparing the spotted test medium against comparative visual indicia depicting lubricating oil in various conditions, and selecting the comparative example which most closely resembles the test medium spotted with the test sample. No chemical reaction occurs between the medium and the fluid, and it is just a visual observation of what the oil looks like compared to a standard.
Markers have been used to identify fluids. Proton accepting chemical substances, that at a solution concentration of below about 50 milligrams per liter, impart little or no significant color to organic solvents, have been proposed as markers, or taggants, especially for petroleum-derived fuels. The marker is dissolved in a liquid to be identified, and then subsequently detected by performing a chemical test on the marked liquid. Markers are sometimes employed by government agencies to ensure that the appropriate tax has been paid on particular grades of fuel. Oil companies also mark their products to help assist in identifying diluted or altered products. These companies often go to great expense to make sure their branded petroleum products meet certain specifications, for example, volatility and octane number, as well as to provide their petroleum products with effective additive packages containing detergents and other components. Consumers rely upon product names and quality designations to assure that the product being purchased is the quality desired. Thus, it is important to be able to identify a marker in a petroleum product.
Traditionally, the presence of a marker substance is detected and optionally quantified by extracting the fuel with an immiscible aqueous or significantly aqueous solution of an acid substance, the precise nature of which can be varied according to the characteristics of the marker substance. The acid reacts with the basic compound to produce a readily visible, more or less intensely colored cation, that is dissolved in the aqueous acid phase. This method is disclosed in U.S. Pat. No. 5,145,573. Additionally, a method has been disclosed in WO 03/078551 A2 where the acidic substance has been applied to a test strip. The test strip is dipped into the oil and diazo-type marker reacts with the acidic substance in the test strip and changes color.
The quantity of marker substance in the extract may also be measured, for instance, by visible light absorption spectrophotometry, the results of which are then compared with a reference standard to determine the original concentration of basic marker in the fluid. It may be necessary to make repeated, typically two or three, extractions of the fluid to recover the entire amount of marker originally present in order for complete quantification. Additionally, the extracted, separated phase is classifiable as a hazardous waste and presents problems of safe and lawful disposal, especially when examinations are made “in the field.” Furthermore, the fluid with which was tested may be contaminated, making return to its original source undesirable and presenting additional waste disposal problems.
It would be desirable to have an accurate and easy analytical method to determine the identity and/or the conditions of a functional fluid. It would further be desirable to have an accurate analytical method to determine the identity and/or the fluid condition in the field.
The present invention will rapidly indicate the identity of and/or the condition of a functional fluid such as lubricating oils, engine oil, automatic and manual transmission fluids, continuously variable transmission fluids, infinitely variable transmission fluids, greases, gear oils, hydraulic fluids, metalworking fluids, antifreeze fluids, coating system fluids, cooling systems fluids, farm tractor fluids, transformer fluids, fuels such as diesel, gasoline, biofuels, emulsified fuels, and the like in the field. Many owners/operators of equipment that depend on these functional fluids currently depend on standard guidelines, such as hours or mileage, to determine the appropriate interval to change the functional fluid or the end of its useful life. Additionally, labs are relied on today to determine the specific identify of a fluid, where a tool that would allow identification in the field would speed warranty resolution. Additionally, various absorbent materials (wipes, shop towels, paper towels, and napkins) are normally used in checking functional fluids. The present invention does not require the use of absorbent materials with a diagnostic functionality as the functional fluid can be used on any surface type material as long as the surface does not chemically interfere with the indicator.
A need exists for a simple and rapid method of chemically analyzing a sample of a fluid on a qualitative basis to determine condition, origin or other useful property. The present invention will rapidly indicate the condition and/or identity of a functional fluid such as lubricating oils, engine oil, automatic and manual transmission fluids, continuously variable transmission fluids, infinitely variable transmission fluids, greases, gear oils, hydraulic fluids, metalworking fluids, antifreeze fluids, coating system fluids, cooling systems fluids, farm tractor fluids, transformer fluids, fuels such as diesel, gasoline, biofuels, emulsified fuels, and the like in the field.
Indicators have been used in analytical methods for monitoring fluids. Generally, redox indicators are sensitive in the presence of air more specifically oxygen and light,. The instability of indicators has made them not useful for analytical tests that monitor fluid conditions. It would be desirable to have a stable delivery system resulting in a stable indicator that is easy to use to determine the condition of a functional fluid. A need exists for a simple and rapid method of chemically analyzing a functional fluid to determine its condition, quality, identity or other useful properties.
It is an object of this invention to provide an easy and convenient delivery system to accurately analyze the condition, quality and identity of a functional fluid. It is a further object of the invention to provide a method to analyze functional fluids rapidly in the field. It is still a further object of the invention to provide a delivery method such as an aerosol, mist, spray, liquid or semi liquid for a stable indicator that can identify reactant byproducts in a functional fluid which thus identifies the quality and condition of the functional fluid. It is still the object of the present invention to provide a method to test the quality or the identity of a functional fluid in the field rapidly by untrained personnel and without precision measurement. It is still a further object of the invention to provide a diagnostic kit for analysis of functional fluids rapidly in the field.
The present invention is a method to determine the condition and/or identity of a functional fluid comprising
The invention further provides a diagnostic kit for the analysis of functional fluids comprising
The present invention provides a method and device such as a kit for analyzing and monitoring the condition or identity of functional fluids. The functional fluids comes from innumerable sources, including internal combustion engines, stationary engines, turbines, transmissions, differentials, pumps, metalworking operations, cooling systems, and the like. The functional fluids include automatic transmission fluids, continuously variable transmission fluids, infinitely variable transmission fluids, traction drive transmission fluids, manual transmission fluids, power steering fluids, antifreeze fluids, lubricating oils, greases, crankcase lubricants, mineral oils, oils with Group 1, 2, 3 or 4 base oils, differential lubricants, turbine lubricants, gear lubricants, gear box lubricants, axle lubricants, farm tractor fluids, transformer fluids, compressor fluids, cooling system fluids, metal working fluids, hydraulic fluids, brake fluids, industrial fluids, fuels, continuously variable transmission fluid, infinitely variable transmission fluid, and the like. In one embodiment, the functional fluid is an automatic transmission fluid. In one embodiment, the functional fluid is a power steering fluid. In one embodiment, the functional fluid is an internal combustion fuel such as gasoline and/or diesel. In one embodiment, the functional fluid is compressor fluids such as air compressor lubricants and/or turbine lubricants. In one embodiment, the functional fluid is an internal combustion engine oil. In one embodiment the functional fluid is tested after some time in use.
In one embodiment, the analysis of an engine oil identifies the total base number (TBN) remaining in the engine oil. Total base number is a useful measure of the quality and life remaining in an engine oil. The depletion of total base number in the engine oil indicates that the useful life of the engine oil is ending and the engine oil needs to be replaced or additized.
The total base number of a typical passenger care motor oil is between about 4 and 9 TBN depending on the initial quality of the engine oil. The total base number of a diesel engine oil is typically between about 4 and 15 TBN depending on the initial quality of the engine oil. When the TBN of an internal combustion engine oil falls to levels about 2 TBN the oil is very close to the end of its useful life and should be replaced, or additized for proper utilization of the oils.
The method of the present invention employs an indicator that analyzes TBN of a functional fluid such as an engine oil. The TBN in the functional fluid that needs to be changed is at least less 0.5 TBN or equal to about 0 TBN unit, in another embodiment less than about 1.0 TBN, and in another embodiment less than about 2.0 TBN, and in another embodiment less than 4.0 TBN, calculated as milligrams of KOH per gram of sample.
In one embodiment, oxidation byproducts occur due to the oxidation of the functional fluid over its life. The analysis of the present invention detects the functional fluids' oxidized species or oxidation byproducts that result from use of the fluid itself. Generally, functional fluids contain oxidation inhibitors in additive packages to prevent and/or delay the oxidation of the functional fluid. The oxidation byproduct and/or oxidizing species generally build up in the functional fluid after the depletion of or reduction of oxidation inhibitors. The oxidizing species and/or oxidation byproducts in the functional fluid demonstrate that the condition of the functional fluid has exceeded its useful life and should be changed for proper utilization of the functional fluid.
The oxidation byproducts/oxidizing species that the redox indicator determines include hydroperoxides, peroxides, oxides of nitrogen, nitrogen oxides, and the like. In one embodiment, the oxidizing byproduct is a peroxide or a hydro peroxide. The method can determine one or more combinations of the oxidation byproducts and/or oxidizing species.
The concentration of oxidation byproducts/oxidizing species in the functional fluid is at least concentration greater than about 150 ppm, in another embodiment greater than about 30 ppm, in another embodiment greater than about 10 ppm, and in another embodiment greater than about 1 ppm calculated as hydrogen peroxide to determine the oxidation byproducts/oxidizing species.
Reagents
The choice of reagent depends on the type of functional fluid being tested and/or the parameters being determined such as the concentration of acidic or basic components, presence or concentration of metals, oxidative/reductive potential, identity markers or the presence of specific components to name a few. Reagents for the purposes of this invention are substances, indicators and/or markers that enable the state of a chemical system to be characterized. The reagents function by a variety of mechanisms both in how the specific parameter is determined in how the indicator responds. The reagents function by a color change as seen through visual examination, colorimetry, photometry, fluorescence, chemiluminescence and the like. The indicators include redox indicators, acid base indicators, metal indicators, absorption indicators, marker indicators and the like. The indicators can be used alone or in combination. In one embodiment the indicator is stable.
The color of the indicator is chosen depending on the type of functional fluid being tested and/or the level of degradation of the functional fluid. Certain colors contrast strongly to the usual color of the functional fluid which is preferred. The choice of a suitable color may be determined by a particular application. For example, in one embodiment automatic transmission fluid for passenger cars is colored red for identification purposes. It would be inappropriate to use an indicator that turns red to indicate an unacceptable condition in the functional fluid of an automatic transmission fluid. For example, in an automatic transmission fluid, a selection of the color indication is in the range of varying blues to greens and mixtures thereof would be desired.
The marker substance is chosen to be compatible with the functional fluid. It may be beneficial for the marker substance to be stable to the service conditions of the fluid, but it is not necessary. In general a marker substance is used to identify new functional fluids. In some cases however, it could be useful to validate the identity of a functional fluid for, as an example, warranty claims. In this case the marker would need to survive and be detectable after experiencing the typical operating conditions of the functional fluid. In the case of markers, the marker is added prior to the functional fluid being used so that the “lock and key” marker indicator system is available to use under the present invention. This additization can be done at the lubricant manufacturer's production facility or by any time prior to performing the “lock and key” method of this invention.
Further, “lock and key” type markers are also included as reagents in this invention. The “lock and key” type markers include where a “lock”, a material soluble in the fluid, which may or may not be stable to the conditions of use depending on the desired time to test for the lock, is added to the functional fluid and a marker, or “key”, is chosen to specifically detect the lock. This may also take the form where a determined functional additive, present in the functional fluid for performance reasons, is targeted and a “key” marker is selected to indicate the presence of the “lock”.
Acid/base (pH) indicators include malachite green, brilliant green, methyl green, picric acid, cresol red, crystal violet, metanil yellow, m-cresol purple, thymol blue, p-xylenol blue, thymol blue sodium salt, quinaldine red, tropaeolin OO, 2,6-dinitrophenol, phloxine B, 2,4-dinitrophenol, 4-dimethylaminoazobenzene, bromochlorophenol blue, bromophenol blue, bromophenol blue sodium salt, congo red, methyl orange, 2,5-dinitrophenol, 1-naphthyl red, bromocresol green, bromocresol green sodium salt, alizarin S, methyl red, methyl red sodium salt, bromophenol red, chlorophenol red, hematoxylin, litmus, bromocresol purple, 4-nitrophenol, bromoxylenol blue, alizarin, bromothymol blue, bromothymol blue sodium salt, nitrazine yellow, phenol red, phenol red sodium salt, cresol red, 3-nitrophenol, neutral red, 1-naphtholphthalein, o-cresolphthalein, phenolphthalein, thymolphthalein, alizarin yellow GG, alkali blue, epsilon blue, indigo carmine, nile blue A and acid fuchsin and the like. Combinations may be used.
Absorption indicators include fluorescein, eosin, phloxine, rose bengal and rhodamine 6G and the like. Combinations may be used.
Metal indicators include alizarin complexone, alizarin S, arsenazo III, aurintricarboxylic acid, 2,2′-bipyidine, bromopyrogallol red, calcon (eriochrom blue black R), calconcarboxylic acid, chrome azurol S, chromotropic acid, disodium salt, cuprizone, 5-(4-dimethylamino-benzylidene)rhodanine, dimethylglyoxime, 1,5-diphenylcarbazide, dithizone, eriochrome black T, eriochrome blue SE, eriochrome blue black B, eriochrome cyanine R, fluorescein complexone, glyoxalibis(2-hydroxylanil), hematoxylin, 8-hydroxyquinoline, 2-mercaptobenzothiazole, methylthymol blue, murexide, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, nitroso-R-salt, 1,10-phenanthroline, phenylfluorone, phthalein purple, 1-(2-pyridylazo)-naphthol, 4-(2-pyridylazo)resorcinol, pyrogallol red, sulfonazo III, 5-sulfosalicylic acid, 4-(2-thiazolylazo)resorcinol, thorin, thymolthalexon, tiron, tolurnr-3,4-dithiol, xylenol orange, zincon and the like. Combinations may be used. In one embodiment the preferred indicator is alizarin for lubricating oils.
Redox indicators include neutral red, safranine T or O, indigo, indigo carmine, methylene blue, thionine, thymolindophenol, 2,6-dichlorophenolindophenol, gallocyanine, nile blue, variamine blue, diphenyl amine, diphenylamine-4-sulfonic acid, barium salt, tris(2,2dipyridyl)iron(II) sulfate, N-phenylanthranilic acid, ferroin, nitroferroin, 5,6-dimethylferroin, 4-amino-4′-methyldiphenylamine, diphenylbenzindine-disulfonic acid, o-dianisidine, 3,3′-dimethylnaphthidine, 3,3′-dimethylnaphthidine disulfonic acid, bis(5-bromo-1,10-phenanthroline)ruthenium(II) dinitrate, tris(5-nitro-1,10-phenanthroline)iron(II) sulfate, Iron(II)-2,2′,2′-tripyridine sulfate, tris(4,7-biphenyl-1,10-phenanthroline)iron(II) disulfate, o,m′-diphenylaminedicarboxylic acid setopaline, p-nitrodiphenylamine, tris(1,10-phenanthroline)-iron(II) sulfate, setoglaucine O, xylene cyanole FF, erioglaucine A, eriogreen, tris(2,2′-bipyridine)-iron(II) hydrochloride, 2-carboxydiphenylamine [N-phenyl-anthranillic acid], benzidine dihydrochloride, o-toluidine, bis(1,10-phenanthroline)-osmium(II) perchlorate, diphenylamine-4-sulfonate Na salt), 3,3′-dimethoxybenzidine dihydrochloride [o-dianisidine], ferrocyphen, 4′-ethoxy-2,4-diaminoazobenzene, N,N-diphenylbenzidine, diphenylamine, N,N-dimethyl-p-phenylenediamine, variamine blue B hydrochloride, N-phenyl-1,2,4-benzenetriamine, Bindschedler's green, 2,6-dichloroindophenol (Na salt), 2,6-dibromophenolindophenol, brilliant cresyl blue [3-amino-9-dimethyl-amino-10-methylphenoxyazine chloride], iron(II)-tetrapyridine chloride, Starch (soluble potato, I3 present), gallocyanine (25° C.), nile blue A [aminonaphthodiethylamino-phenoxazine sulfate], indigo-5,5′,7,7′-tetrasulfonic acid (Na salt), Indigo-5,5′,7-trisulfonic acid (Na salt), indigo-5,5′-disulfonic acid (Na salt), phenosatranine, Indigo-5-monosulfonic acid (Na salt), bis(dimethylglyoximato)-iron(II) chloride, induline scarlet, and the like. In one embodiment, the redox indicators are methylene blue, p-nitrodiphenyl-amine, N,N-diphenylbenzidine, diphenylamine, neutral red and the like. In one embodiment, the redox indicator is methylene blue.
The redox indicators may already be in a reduced form or in reduced in solutions using reducing agents such as phosphoric acid, dithiophosphoric acid, sodium borohydride, aluminium hydride and the like. The reducing agents may be used alone or in combination. In one embodiment, the reducing agent is used in the range of about equal to or ≧1 equivalent based on the amount of redox indicators being reduced.
Often a combination of an acid and a reducing agent may be used along with the redox indicator. One agent may be both as with a dithiophosphoric acid, or two separate materials may be used. For example, along with the redox indicator such as methylene blue, one might use hydrochloric acid (HCL) and sodium thiosulfate. Other examples and acid and the reducing agent combination might be sodium bisulfate (NaHSO4) and a zinc dialkyldithiophosphate (ZDDP), or phosphoric acid (H3PO4) and ZDDP. Another example of a single reagent providing both the acid and reducing agent would be sodium bisulfite (NaHSO3). Any of these may optionally include a catalytic metal ion of metals such as Cu, Fe, Mo or Mn. In some instances the amount of reducing agent is in excess of the redox indicator material, by a stoichiometric factor of 1.1, 1.5, 2 or 10 for example. The excess or reserve reduction potential adds additional stability to the indicator system.
In one embodiment, about 0.5 wt. % methylene blue is prepared in a solution of isopropyl alcohol. To that solution is added excess of about 2.5 equivalents of di(2-ethylhexyl)dithiophosphoric acid resulting in the methylene blue reduced to its colorless form (II). The excess of the dithiophosphoric acid forms a salt of the reduced methylene blue and stabilizes it. This solution is applied to a test medium. The solvent is evaporated to provide a redox indicator test medium used to effectively evaluate functional fluids for oxidizing species and/or oxidizing byproducts such as peroxide.
Marker substances include diazo dyes, anthraquinone dyes and the like, metals, metal salts, metal oxides, metal coordination complexes and the like or other substances compatible with the lubricant. It may be beneficial for the marker substance to be stable to the service conditions of the fluid, but it is not necessary. In general marker substances are used to identify new fluids. In some cases however, it could be useful to validate the identity of a functional fluid for, as an example, warranty claims. In this case the marker would need to survive and be detectable after experiencing the typical operating conditions of the functional fluid. Combinations of these substances may be used.
Developing agents are substances that will make conspicuous the presence or absence of a marker substance. Developing agents could include mineral or organic acids, organic or mineral bases or basic substances, oxidizing agents, reducing agents, chelating agents and the like. Combinations of developing agents may be used.
Optionally, in preparing the reagents, stabilizers may be added. The stabilizers include inhibitors such as para-amino benzoic acid, phenyl alpha-napthal amines and the like. Another class of stabilizers includes acids such as hydrochloric acid, dithio-phosphoric acid, phosphoric acid, thio-phosphoric acids. Another class of stabilizers includes bases such as sodium hydroxide, sodium bicarbonate, potassium hydroxide, and the like. Another class of stabilizers includes buffer solutions which are most commonly aqueous solutions of a weak acid and its conjugate base or a weak base and its conjugate acid, to maintain the pH of the reagents as necessary. The stabilizers can be used alone or in combination. The stabilizer is employed in the range 1 equivalent to or greater than the amount of indicator being reduced.
Each type of indicators can be used alone or in combinations. Further, the indicators may be a combination of indicators or one indicator. Each type of indicators are used in the range of about 0.001 wt. % to about 5 wt. %, and in another embodiment are used in the range of about 0.05 wt. % to about 2 wt. % and in another embodiment are used in the range of about 0.1 wt. % to about 1 wt % in the aerosol solution applied to the medium.
Substrate or Medium
The functional fluid to be tested is placed upon any surface or medium. This surface or medium includes absorbent material, nonabsorbent material and combination thereof. The medium includes paper, cellulosic material such as cellulose, cellulose nitrate, cellulose acetate, cellulosic material, wood, paper, chromatography paper, filter paper, polymeric fibers, natural fibers, finely woven fabrics, metal, glass, glass micro fiber, sintered glass, silica and/or alumina coated surfaces such as thin layer chromatography plates, plastic, plastic laminated material, composites, cotton (such as shop rags), cloth, and combinations thereof. Other absorptive/adsorptive materials, having the, general physical properties and characteristics of chromatography paper are also be acceptable. The medium must be capable of receiving a sample of the functional fluid but is not necessarily absorbent. The medium should be compatible with the specific indicator and/or developing agent; that is, in one embodiment it should not promote oxidation or acid-base reactions.
In one embodiment the preferred medium includes “Whatman” white colored chromatography paper or filter paper in the form of an easy to dispense and use wipe. In one embodiment, absorptive paper, such as chromatography paper is preferred, in particular for lubricating oil samples. Light colored chromatography paper provides a consistent background which contrasts well with the functional fluid, provides for a more conspicuous color change and has the proper adsorptive affinity for the various components of an oil. For example, the coloration of the indicator becomes more pronounced over time on the outer edges of the sample spot on the paper as the indicator colored portion of the mixture is swept along with the mobile phase (oil and solvent) faster than the darker components of the used oil, such as sludge. This is due to the differences in adsorptive affinity for the paper. This difference in affinity becomes important as the concentration of sludge in the oil sample increases over the service life.
It is to be understood that depending on the type of functional fluid being analyzed and the particular functional purpose of the fluid, for instance, whether for gasoline powered engines as opposed to diesel powered engines, the test medium may need to be varied, whether the medium is chromatography paper or other type of paper, polymeric fiber material or nonabsorbent material like glass, plastic or metal. The medium may differ in its adsorptive affinity for the various components in the particular fluid, porosity, density, wicking ability, or other physical characteristics such as color.
Light colored media provides a consistent background which contrasts well with most functional fluids, and provides for a more conspicuous color change and has the proper adsorptive affinity for the various components of the functional fluid. For example, the coloration of the redox indicator becomes more pronounced over time on the outer edges of the sample spot on the paper as the indicator colored portion of the mixture is swept along with the mobile phase (functional fluid and solvent) faster than the darker components of the used functional fluid, such as sludge. This is due to the differences in adsorptive affinity for the paper. In one embodiment, the test medium is white. In one embodiment the medium includes “Whatman” white colored chromatography paper or filter paper in the form of an easy to dispense and use wipe.
The medium may differ in its adsorptive affinity for the various components in the particular functional fluid, such as porosity, density, wicking ability, or other physical characteristics such as color.
The shape of the medium is unimportant, so long as it is of an effective size to permit dispersion of the functional fluid sample, but small enough to be economical and limit waste.
Solvents
Suitable solvents may be used with the reagents. The solvent used depends on the type of functional fluid being tested, the aerosol propellant and system (can, actuator and valve) being used and the indicator being used. Combinations of solvents are also useful when the indicator, depending on the application and type of analysis desired, is not soluble in the functional fluid. Particularly, solvents or combinations of solvents which present a desirable combination of properties including good solvency power and miscibility with the functional fluid and the redox indicator, low vapor pressure at ambient temperatures, high flash points and the like.
Solvents include aliphatic, unsaturated and aromatic hydrocarbons, alcohols, glycols, glycol ethers, lower alcohols, such as methanol, ethanol and propanol, ethers, esters, amides, water and the like. Combination of solvents may be used.
The solvent is used in the range of about 1% to about 99.9%, in one embodiment about 5% to about 98% and in another embodiment about 1% to about 95.5% of the reagent solution.
Optional Components
Optional components may be added to the indicator solutions. These include surfactants to help media wetting, maskants and fragrances to improve customer appeal, antifoam additives to improve product manufacture and use, acids and bases to adjust the ph of the indicator solutions and buffers to maintain the pH of the indicator solutions. The optional components can be used alone or in combination.
Examples of surfactants include ionic, anionic (based on sulfate, sulfonate or carboxylate anions), sodium dodecyl sulfate (sds), ammonium lauryl sulfate, and other alkyl sulfate salts, sodium laureth sulfate, also known as sodium lauryl ether sulfate (sles), alkyl benzene sulfonate, soaps, or fatty acid salts, cationic (based on quaternary ammonium cations), cetyl trimethylammonium bromide (ctab) a.k.a. hexadecyl trimethyl ammonium bromide, and other alkyltrimethylammonium salts, cetylpyridinium chloride (cpc), polyethoxylated tallow amine (poea), benzalkonium chloride (bac), benzethonium chloride (bzt), zwitterionic (amphoteric), dodecyl betaine, dodecyl dimethylamine oxide, cocamidopropyl betaine, coco ampho glycinate, nonionic, alkyl poly(ethylene oxide), alkyl polyglucosides, including: octyl glucoside, decyl maltoside, fatty alcohols, cetyl alcohol, oleyl alcohol, cocamide mea, cocamide dea, cocamide tea, neodol 25, fatty alcohols, ethoxylated alcohols, alkyl polyglucosides, triton bg-10 surfactant, triton cg-110 surfactant, branched secondary alcohol ethoxylates, tergitol tmn series, ethylene oxide/propylene oxide copolymers, tergitol I series, tergitol xd, xh, and xj surfactants, triton cf surfactants, triton df surfactants, tergitol minfoam surfactants, nonylphenol ethoxylates, tergitol np series, octylphenol ethoxylates, triton x series, secondary alcohol ethoxylates, tergitol 15-s series, triton ca surfactant, triton n-57 surfactant, triton x-207 surfactant, surfynol surfactants, primary amines, tertiary amines, monoalkyl and polyamines, ethoxylated amines, ethoxylated diamines, propoxylated amines, amine salts, quaternary ammonium salts, ethoxylated quaternary salts, propoxylated quaternary salts, amine oxides, amides, ethoxylated amides, esters: nonionic surfactants: ethoxylated fatty acids, amphoteric compounds, sulfosuccinates and sulfosuccinimates, fatty acid esters, fatty alcohols, alkanolamides, alkyl and alkyl ether sulfates, lauryl sulfates and lauryl ether sulfates, alkyl aryl sulfonates and alpha olefin sulfonates, alkoxylated nonionic surfactants, soya lecithins, alkyl sulfates, alkyl ether sulfates, imidazolines, alkanolamides, dowfax anionic surfactants, Dupont sulfonates, zonyl fluorosurfactants, peg esters and glyceryl esters, sorbitan esters/sorbitan ester ethoxylates, silicone surfactants, naphthalene condensates, sodium alkylnaphthalene sulfonates, pegol block copolymers, alkyl pyrrolidones, alkyl and glycol esters, emerest and trydet ethoxylated fatty acids and polyethylene glycol fatty acid esters, pilot hydrotropes, aristonate petroleum sulfonates, aristol sulfonatable oils, amido-amines, betaine amphoterics imidazolines imidazolinium amphoterics sulfosuccinates, fatty acid diethanolamides, neodol alcohols and the like. The surfactants can be used alone or in combination.
Examples of maskants and fragrances include abbarome 011, acalea tt, allyl amyl glycolate, ambrettolide, amyl cinnamic aldehyde, amyl salicylate, andrane, anethole 21/22, anethole usp, anethole usp, aphermate, apo patchone, bacdanol, benzyl butyrate, benzyl propionate, benzyl salicylate, bicyclononalactone, bornafix, canthoxal, cashmeran, cassiffix, cedramber, cedrenyl acetate, celestolide, cinnamalva, citral dimethyl acetal, intarome cotton odorsynthesis, intarome lavender musk odorsynthesis, citronalva, citronellol 700 jax, citronellol 750, citronellol 950, citronellol coeur, citronellyl acetate a, citronellyl acetate coeur, citronellyl acetate pure, citronellyl formate, clarycet, clonal, coniferan, cyclabute, cyclacet, cyclaprop, cyclemone a, cyclobutanate, cyclogalbaniff, cyclohexyl ethyl acetate, cyclohexyl ethyl alcohol, damascol 4, decyl methyl ether, delta damascone, dihydro cyclacet, dihydro floralate, dihydro floralol, dihydro myrcenyl acetate, dihydro terpineol, dihydro terpinyl acetate, dihydro terpinyl acetate dsa, dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate, dimethyl benzyl carbinyl butyrate, dimethyl cyclormol, dimethyl octanol, dimethyl phenyl ethyl carbinyl acetate, dimyrcetol, diola, dipentene 5100, dulcinyl recrystallized, ethyl ortho methoxy benzoate, ethyl phenyl glycidate, fleuramone, fleuranil, floralate, floralol, floralozone, fraistone, fructone, galaxolide 50 bb, galaxolide 50 dep, galaxolide 50 dpg, galaxolide 50 ipm, galbanum coeur, gelsone, geraldehyde, geraniol 5020, geraniol 7030, geraniol 980 pure, geraniol coeur, geranyl acetate a, geranyl acetate extra, geranyl acetate pure, grisalva, helional, herbac, hexalon, hexenyl salicylate, cis-3, hexyl acetate, hexyl cinnamic aldehyde, hexyl salicylate, hyacinth body, hyacinth body no.3, hydratropic aldehyde dimethyl acetal, hydroxyol, hypo-lem, indolarome, indolene 50, intreleven aldehyde, intreleven aldehyde special, ionone 100%, ionone alpha, ionone alpha beta regular, ionone beta, iso amyl butyrate, iso amyl salicylate, iso bornyl propionate, iso butyl quinoline, iso cyclemone e, iso cyclo citral, iso cyclo geraniol, iso e super, isoproxen, jasmal, jasmelia, jessemal, kharismal, koavone, kohinool, lavonax, lemsyn, liffarome, lindenol, lyral, lyrame, lyrame super, maritima, meijiff, melafleur, methyl cedryl ketone chinese, methyl cinnamic aldehyde alpha, methyl ionone gamma a, methyl ionone gamma coeur, methyl ionone gamma pure, methyl lavender ketone, montaverdi, muguesia, muguet aldehyde, muguet aldehyde 50 bb50, myrac aldehyde, myrcenol super, myrcenyl acetate, neoproxen, nerol 800, nerol 850, nerol 900, neryl acetate jax, ocimene, ocimenyl acetate, octacetal, orange flower ether, orivone, orriniff 25% ipm, oxaspirane, ozofleur, pamplefleur, peomosa, phenafleur, phenoxanol, phenoxyethyl iso butyrate, phenoxyethyl propionate, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl benzoate, phenyl ethyl formate, phenyl ethyl iso butyrate, phenyl ethyl salicylate, piconia, precyclemone b, prenyl acetate, proflora, pseudo linalyl acetate, reseda body, rosalva, rosamusk, roseate, rosemarel, salicynalva, sanjinol, santaliff, spirodecane, strawberiff, styralyl propionate, syvertal, terpineol 900, terpineol alpha jax, terpineol extra, terpinolene 20, terpinolene 90, terpinolene 90 pq, terpinyl acetate extra, terpinyl acetate jax, tetrahydro muguol, tetrahydro muguol coeur, tetrahydro myrcenol, tetrameran, tobacarol, triplal, unipine 60, unipine 85, vandor b, vanoris, verdol, verdox, verdox hc, verdural b extra, verdural extra, vertenex, vertenex hc, vertofix coeur, vertoliff, vigoflor, violiff, and mixtures thereof, also included in maskants are additives that act as odor scavengers such as amine scavengers and hydrogen sulfide scavengers like epoxides, basic amines, and the like. The maskants and fragrances can be used alone or in combination.
Examples of antifoams/defoamers are polysiloxanes, esters, insoluble oils, mineral oils, surfactants, amorphous silica, silicone emulsions, and the like. The antifoams/defoamers can be used alone or in combination.
Examples of acids include perchloric acid, hydroiodic acid, hydrobromic acid, hydrochloric acid, sulfuric acid, nitric acid, hydronium ion, chloric acid, bromic acid, perbromic acid, iodic acid, and periodic acid, fluoroantimonic acid, magic acid FSO3HSBF5, carborane superacid H(CHB11CL11), fluorosulfuric acid FSO3H, triflic acid CF3SO3H , phosphoric acid, carboxylic acids, phenol, aromatic acids and the like. This can also include acidic buffer solutions. The acids can be used alone or in combination.
Examples of bases include potassium hydroxide, barium hydroxide, cesium hydroxide, sodium hydroxide, strontium hydroxide, calcium hydroxide, lithium hydroxide, rubidium hydroxide, butyl lithium, lithium diisopropylamide, sodium amide, sodium hydride, sodium carbonate, potassium carbonate, magnesium carbonate, ammonium carbonate, alanine, ammonia, NH3 magnesium hydroxide, Mg(OH)2, amine bases such as: methylamine, pyridine and the like. The bases can be used alone or in combination.
Examples of aqueous buffers include combinations of ammonium chloride and ammonia, formic acid and sodium formate, acetic acid and sodium acetate, and the like. The aqueous buffers can be used alone or in combination.
The optional component is used in the range of about 0% to about 20% wt, in one embodiment about 0.01% to about 5% wt, and in another embodiment about 0.1% to about 2% wt of the reagent solution.
Propellants
The reagent solution can be sprayed onto the test media with a pump type sprayer or can be sprayed from an aerosol can. The propellant used must be compatible with the reagents. In one embodiment, the propellant is oxygen free or substantially free of oxygen. For example, with redox indicators the propellant should be oxygen free and chemically/oxidatively inert. Inert propellants include nitrogen, hydrocarbons, propane and butane, chlorofluorocarbons (CFCs), hydrocarbons, propane, n-butane and isobutene, dimethyl ether (DME) and methylethyl ether, nitrous oxide, hydrofluoroalkanes (HFA), HFA 134a (1,1,1,2-tetrafluorethane), HFA 227 (1,1,1,2,3,3,3-heptafluoropropane), saturated light hydrocarbons, C3-C6 (e.g., propane, isobutene, nbutane), CFC-11, HCFC-22, HCFC-142b, dimethyl ether CFC-11, HCFC-22, HCFC-142b, HCFC-152a, HFC-125, CFC-11, HCFC-22, HCFC-142b, HFC-227 ea, CFC-11, CFC-12, CFC-114, HCFC-22, HCFC-142b, compressed gases (carbon dioxide, air, nitrogen, nitrous oxide), SF6, fluorinated dimethyl ethers, Bis(difluoromethyl)ether, vinyl chloride monomer, and mixtures thereof. In one embodiment the propellant is free of halogens. Combinations of propellants may be used.
Liquids/Semi Liquids
In a liquid or semi liquid delivery system, the reagent solution is in a liquid or semi liquid form. Generally, a liquid is a form of matter intermediate between gases and solids, in which the molecules are much more highly concentrated than gases, but much less than solids. Generally a semi liquid is a material that has an increased viscosity over a liquid substance. Generally, this increased viscosity is the result of the addition of materials that increase viscosity such as viscosity modifiers, polymers, tackifiers, clays, fillers, thickeners, rheology modifiers and the like. Semi liquids include gels, emulsions, suspensions, dispersions, additized liquids and the like. The container is any container capable of dispensing the liquid or semi liquid. The dispensing systems place the reagent solution onto the sample or in another embodiment the medium with the sample onto the reagent solution. Dispensing systems for liquids and/or semi liquids include droppers, squeeze containers, pour containers, pipettes, pumps without propellants, sprays without propellants, rollers, brushes, dipping and the like.
Visual Indicia
Analysis in particular qualitative analysis of the reacted test sample is accomplished by visual inspection of the reacted test sample using a provided visual indicia as a guide. Analysis occurs after an effective period of time to allow for the reaction between the components of the functional fluid and the reagents. Generally the time for reaction is in the range of about 0.01 sec. to about 1 hour, in another embodiment about 30 sec. minute to about 30 minutes, in another embodiment about 1 minute to about 15 minutes, and in another embodiment about 1 minute to about 5 minutes. In the embodiment, the time for the reaction is immediate.
The visual indicia include an artistic rendering, a reproduction of a photograph of a functional fluid in various conditions with and without the reagent; for example, oxidizing species and/or oxidization byproducts, color key, a written description of the color change and the like. Combinations of visual indicia may be used. The visual indicia generally include one representation, two representations and more than two representations of the functional fluid disposed upon the media in various conditions with and without the reagent; for example, oxidizing species and/or oxidization byproducts. In one embodiment the preferred visual indicia is one in an unacceptable condition containing oxidizing species and/or oxidization byproducts and one in acceptable condition. A descriptive text corresponding to each of these examples may be provided.
In one embodiment the visual indicia depicted is dispersed upon the same or similar medium provided in the kit, to assure that the kit user compares the sample to be tested to examples produced under similar conditions. It is to be understood that a different number of indicia may be provided.
Method
The method comprises the steps of (a) obtaining a sample of a functional fluid, (b) contacting the sample of the functional fluid with a medium, (c) spraying, misting, atomizing and/or contacting the appropriate reagent solution on the media that contains the sample of the functional fluid to be tested, (d) waiting for an effective period of time to allow for the reaction between the components of the functional fluid and the indicator in the reagent system, and (e) making a visual determination of the sample of the functional fluid on the medium using the printed instructions and/or comparative visual indicia depicting the functional fluid (in various) conditions
It is not necessary that the sample be taken during actual operation of the engine or other equipment or machinery in order to obtain a representative sample of the functional fluid. The sample of functional fluid may be taken at any time before, during or after operation of the engine or equipment. The functional fluid sample can be new, used or combinations thereof. In one embodiment the functional fluid test is especially useful during or after operation for some period of time.
The diagnostic kit contains a means to apply the indicator solution, which includes a dropper, pipette, squeeze container, pour container, brush, pumps, dipper container, an aerosol can (which includes the actuator, valve, and optionally an agitator ball) or spray pump that can be sealed containing the reagent solution comprising a base indicator, an acid indicator, a metal indicator, a marker indicator and mixtures thereof and further includes written instructions and/or a set of visual indicia depicting samples of the functional fluid disposed upon a medium printed in color on the package with descriptive text. In one embodiment, the diagnostic kit includes the media upon which the functional fluid sample is placed for testing. In one embodiment, the visual indicia shows a depiction of the functional fluid which is in an acceptable condition (i.e. light color) and also in an unacceptable condition (i.e. dark color).
The analysis of the condition of a functional fluid, for instance an automotive transmission fluid, is essentially dependent upon the reaction of components; i.e., oxidation byproducts in the functional fluid, with a redox indicator. For instance, automotive transmission fluid, as it is used, becomes oxidized forming oxidation byproducts and its inhibitor package becomes depleted, and there may be wear debris from the depletion of the anti-wear additives. During the service life of the automatic transmission fluid a point is reached where these components fall below a minimum acceptable level rendering the automatic transmission fluid unacceptable for further use. Continued use of an unacceptable automatic transmission fluid may cause damage to the transmission. When a sample of used automatic transmission fluid is obtained and the sample is placed upon a suitably treated medium, the oxidative inhibitor additives in the automatic transmission fluid, if they have been consumed or depleted allow for oxidative species in the fluid such as perioxide which will react with the redox indicator changing its color from colorless to various shades of blue or green depending on the concentration of the oxidizing species and presence of metal contaminants. The greater the concentration of oxidizing species, the more color change occurs. The presence or absence of a color change and the relative intensity of the color provides a means for qualitative analysis of the test sample.
For the analysis of the condition of a functional fluid, for instance as engine oil, under this invention is essentially dependent upon the reaction of components in the oil with an appropriate indicator. Engine oil, as it is used, becomes contaminated with acidic byproducts from oxidation, acidic components from fuel combustion and a component of sludge. The chemically basic additives, including detergents, which are added to the oil to neutralize these acidic components, are consumed over time. During the service life of the oil a point is reached where these basic components fall below a minimum acceptable level rendering the oil unacceptable for further use. Continued use of an unacceptable oil will likely cause damage to the engine. When a sample of used oil is obtained and the sample is placed upon a medium and treated with an indicator in a reagent solution, the basic additives in the oil, if they have not been consumed, will react with the indicator changing its color. The presence or absence of a color change and the relative intensity of the color provides a means for qualitative analysis of the test sample.
In one embodiment the functional fluid is an engine oil. The engine oil sample under ordinary circumstances may be obtained using a dipstick provided as a part of the engine, transmission or other equipment under lubrication. The user will withdraw an amount of oil along with the dipstick and the dipstick may then be wiped on the medium or the oil which will collect into a drop at the end of the dip stick may then placed upon the medium. Typically, less that 1 milliliter of oil is necessary for the analysis. Once the oil test sample has been placed on the medium, the sample spot is sprayed with the indicator aerosol and the indicator immediately begins to react. The user allows for an effective period of time to allow for the reaction between the components of the fluid and the indicator. Next, the user determines whether or not a color change occurred, and refers to the visual indicia as a guide. The user may consult the descriptive text accompanying the example selected to determine the condition or identity of the functional fluid.
The marking/identification of a functional fluid, for instance an automatic transmission fluid or automotive engine oil, is desirable because counterfeiting and adulteration/dilution of genuine functional fluids is a large concern of fluid suppliers as counterfeiting and adulteration results in a loss of profits, customer durability problems with vehicles, customer warranty claims, etc. due to a lack of adequate lubricant performance. A simple, easy to use marker system is beneficial since different functional fluids are usually indistinguishable visually. Chemical analyses or physical properties can tell various functional fluids apart but these analyses require expensive laboratory test equipment and often take too long to be a practical end user identification test. The disclosed “lock” and “key” aerosol/spray technology enables an end user to exclude a counterfeit or adulterated product based on a color change resultant from the reaction between a known “lock” added to a functional fluid to yield a “marked” fluid and a “key” reagent present in the aerosol or spray which reacts with the “lock” reagent to give a predictable color change upon contact.
A sample of the functional fluid to be tested is applied to a medium as described below. The results are analyzed visually after the functional fluid on the medium has reaction with the reagent in the aerosol, mist or liquids.
The Indicator solutions of a reagent is prepared at room temperature as follows:
The indicator solutions of a reagent is prepared at room temperature as follows:
Drain samples were taken from the automatic transmissions (“AT”) of 29 vehicles and evaluated using the general method as in Example 1. A good correlation was observed between mileage on the AT fluids, wear metals (Fe, Pb, Cu) as determined by ICP emission spectroscopy analysis, and the observed colors produced on the media as in Example 1 as seen in Table 1.
The total wear metals are the sum of the percents of Cu, Fe, and Pb in the automatic transmission fluid. A green result indicates a fluid in bad condition, blue result indicates a fluid that needs to be changed and red is a fluid in good condition.
This example tests the quality of passenger car engine oil and consists of a substrate of “Whatman” filter paper and an aerosol indicator solution made up of ethanol or isopropanol (90% w/w), lauryl alcohol (10% w/w) and pH indicator (0.1% w/w). The pH indicator used is Alizarin (1,2-dihydroxyanthraquinone).
A used motor oil sample is placed on the dry “Whatman” filter paper and sprayed with the indicator solution. The basic additives (quantified as the TBN or Total Base Number, measured by ASTM D4739) of the oil react with the pH indicator inducing a color change from yellow to purple, with the indicator listed above, to a degree depending on the level of TBN. The intensity of the color change is reduced as the TBN drops over the service life of the oil until no purple color is apparent indicating the fluid has reached its maximum life. (See Table 2)
The results in Table 2 demonstrate that an oil can be analyzed by visual indicia depicting the quality of the oil, as the brown color with no purple at 6000 miles indicates the condition of the oil.
The marker and marker Indicator solutions were prepared at room temperature as follows:
Marker:
Marker Indicator Solution:
The Marker and marker Indicator solutions were prepared at room temperature as follows:
Marker:
Marker Indicator Solution:
While the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention, with the scope of the present invention being defined by the following claims.
