Disclosed are dispersed hydrated potassium borate compositions, as well as additive packages and finished oil compositions comprising the same. The dispersed hydrated potassium borate compositions of the invention exhibit low turbidity and the finished oil compositions exhibit improved wear performance under high temperature conditions.

This invention is directed, in part, to novel dispersed hydrated potassium borate compositions, as well as additive packages and finished oil compositions comprising the same. The dispersed hydrated potassium borate compositions of this invention exhibit low turbidity and the finished oil compositions comprising such dispersed hydrated potassium borate compositions exhibit improved wear protection under high temperature conditions.
The following references are cited in this application as superscript numbers:
1 Peeler, U.S. Pat. No. 3,313,727, Alkali Metal Borate E P. Lubricants, issued Apr. 11, 1967
2 Adams, U.S. Pat. No. 3,912,643, Lubricant Containing Nelutralized Alkali Metal Borates, issued Oct. 14, 1975
3 Sims, U.S. Pat. No. 3,819,521, Lubricant Containing Dispersed Borate and a Polyol, issued Jun. 25, 1974
4 Adams, U.S. Pat. No. 3,853,772, Lubricant Containing Alkali Metal Borate Dispersed with a Mixture of Dispersants, issued Dec. 10, 1974
5 Adams, U.S. Pat. No. 3,997,454, Lubricant Containing Potassium Borate, issued Dec. 14, 1976
6 Adams, U.S. Pat. No. 4,089,790, Synergistic Combinations of Hydrated Potassium Borate, Antiwear Agents, and Organic Sulfide Antioxidants, issued May 16, 1978
7 Adams, U.S. Pat. No. 4,163,729, Synergistic Combinations of Hydrated Potassium Borate, Antiwear Agents, and Organic Sulfide Antioxidants, issued Aug. 7, 1979
8 Frost, U.S. Pat. No. 4,263,155, Lubricant Composition Containing an Alkali Metal Borate and Stabilizing Oil-Soluble Acid, issued Apr. 21, 1981
9 Frost, U.S. Pat. No. 4,401,580, Lubricant Composition Containing an Alkali Metal Borate and an Ester-Polyol Compound, issued Aug. 30, 1983
10 Frost, U.S. Pat. No. 4,472,288, Lubricant Composition Containing an Alkali Metal Borate and an Oil-Soluble Amine Salt of a Phosphorus Compound, issued Sep. 18, 1984
11 Clark, U.S. Pat. No.4,534,873, Automotive Friction Reducing Composition, issued Aug. 13, 1985
12 Brewster, U.S. Pat. No. 3,489,619, Heat Transfer and Quench Oil, issued Jan. 13, 1970
13 Salentine, U.S. Pat. No. 4,717,490, Synergistic Combination of Alkali Metal Borates, Sulfur Compounds, Phosphites and Neutralized Phosphate, issued Jan. 5, 1988
All of the above patents are herein incorporated by reference in their entirety to the same extent as if each individual patent was specifically and individually indicated to be incorporated by reference in its entirety.
High load conditions often occur in gear sets such as those used in automobile transmissions and differentials, pneumatic tools, gas compressors, centrifuges, high-pressure hydraulic systems, metal working and similar devices, as well as in many types of bearings. When employed in such environments, it is conventional to add an extreme-pressure (E.P.) agent to the lubricant composition and, in this regard, alkali metal borates are well known extreme-pressure agents for such compositions.1-11, 13 E.P. agents are added to lubricants to prevent destructive metal-to-metal contact in the lubrication of moving surfaces. While under normal conditions termed xe2x80x9chydrodynamicxe2x80x9d, a film of lubricant is maintained between the relatively moving surfaces governed by lubricant parameters, and principally viscosity. However, when load is increased, clearance between the surfaces is reduced, or when speeds of moving surfaces are such that the film of oil cannot be maintained, the condition of xe2x80x9cboundary lubricationxe2x80x9d is reached; governed largely by the parameters of the contacting surfaces. At still more severe conditions, significant destructive contact manifests itself in various forms such as wear and metal fatigue as measured by ridging and pitting. It is the role of E.P. additives to prevent this from happening. For the most part, E.P. agents have been oil soluble or easily dispersed as a stable dispersion in the oil, and largely have been organic compounds chemically reacted to contain sulfur, halogen (principally chlorine), phosphorous, carboxyl, or carboxylate salt groups which react with the metal surface under boundary lubrication conditions. Stable dispersions of hydrated metal borates have also been found to be effective as E.P. agents.
Gear sets have been subject to ever increasing demands including requirements for satisfactory performance at high temperatures, e.g., greater than 135xc2x0 C. and preferably at least 163xc2x0 C. In turn, this has placed an ever increasing requirement that the E.P. lubricant composition employed in such gear sets provide satisfactory wear and metal fatigue as measured by ridging and pitting requirements of the gear set when evaluated at such high temperatures.
In addition, because hydrated alkali metal borates are insoluble in lubricant oil media, it is necessary to incorporate the borate as a dispersion in the oil and homogenous dispersions are particularly desirable. The degree of formation of a homogenous dispersion can be correlated to the turbidity of the oil after addition of the hydrated alkali metal borate with higher turbidity correlating to less homogenous dispersions. In order to facilitate formation of such a homogenous dispersion, it is conventional to include a dispersant in such compositions. Examples of dispersants include lipophilic surface-active agents such as alkenyl succinimides or other nitrogen containing dispersants as well as alkenyl succinates.1-4, 12 It is also conventional to employ the alkali metal borate at particle sizes of less than 1 micron in order to facilitate the formation of the homogenous dispersion.11 Notwithstanding the use of such additives, lubricant compositions comprising such potassium borates can possess unacceptable turbidity.
In view of the above, lubricant compositions comprising a hydrated potassium borate and which possessed low turbidity and acceptable wear and fatigue properties as measured by pitting and ridging, especially when the gear set is operated at high temperature, would be particularly advantageous.
This invention is directed to the novel and unexpected discovery that reduced wear and fatigue as measured by ridging and pitting in gear sets can be achieved by the use of a lubricant composition comprising a dispersed hydrated potassium borate composition having a specific degree of dehydration.
In addition, this invention is directed to the novel and unexpected discovery that these compositions exhibit acceptable turbidity as evidenced by a turbidity value of less than 300 ntu.
Accordingly, in one of its composition aspects, this invention is directed to a dispersed hydrated potassium borate composition comprising a hydrated potassium borate, a dispersant, optionally a detergent, and an oil of lubricating viscosity wherein said dispersed hydrated potassium borate composition is characterized by a hydroxyl:boron ratio (OH:B) of from at least 1.2:1 to 2.2:1, a potassium to boron ratio of from about 1:2.75 to 1:3.25 and a turbidity value of less than 300 ntu.
In one preferred embodiment, the hydroxyl:boron ratio is from about 1.3:1 to 2.1:1; more preferably, from about 1.3:1 to 2.0:1; and even more preferably, from about 1.3:1 to 1.9:1.
In another preferred embodiment, the dispersed potassium borate compositions described herein have a turbidity of less than about 75 ntu, more preferably, less than about 60 ntu, and still more preferably, less than about 40 ntu.
In still another preferred embodiment, the dispersed hydrated potassium borate composition has a potassium to boron metal ratio of from about 1:2.9 to about 1:3.1 and more preferably about 1:3.
In yet another preferred embodiment, the dispersed hydrated potassium borate composition has an average particle size of less than about 0.6 microns and more preferably from about 0.10 to about 0.30 microns.
Optionally, the dispersed potassium borate compositions contain small amounts of a water-soluble oxo anion. Only from 0.001 moles to 0.11 moles of water soluble oxo anion should be present per mole of boron atom. This water-soluble oxo anion can include nitrate, sulfate, carbonate, phosphate, pyrophosphate, silicate, aluminate, germanate, stannate, zincate, plumbate, titanate, molybdate, tungstate, vanadate, niobate, tantalate, uranates, or can include the isopolymolybdates and isopolytungstates, or the heteropolymolybdates and heteropolytungstates, or mixtures thereof.
Preferably the dispersant in said potassium borate compositions is selected from the group consisting of a polyalkylene succinimide, a polyalkylene succinic anhydride, a polyalkylene succinic acid, a mono- or di-salt of a polyalkylene succinic acid and mixtures thereof. Optionally, the dispersed potassium borate composition contains a detergent such as a metal sulfonate, preferably an alkylaromatic or polyisobutenyl calcium sulfonate or other Group II metal sulfonate that acts in these compositions to help provide for a homogeneous dispersion.
Another aspect of this invention is directed to additive packages comprising from about 10 to 80 weight percent of the dispersed hydrated potassium borate composition described above and from about 90 to 20 weight percent of one or more of conventional additives selected from the group consisting of ashless dispersants (0-10%), detergents (0-5%), sulfurized hydrocarbons (0-40%), dialkyl hydrogen phosphates (0-15%), zinc dithiophosphates (0-20%), alkyl ammonium phosphates and/or thio- dithiophosphates (0-20%), phosphites (0 to 10%), fatty acid esters of polyalcohols (0-10%), 2,5-dimercaptothiadiazole (0-5%), benzotriazole (0-5%), dispersed molybdenum disulfide (0-5%), foam inhibitors (0-2%), and imidazolines (0-10%) and the like wherein each weight percent is based on the total weight of the composition. It is understood, of course, that the addition of such conventional additives will dilute the concentration of the hydrated potassium borate, dispersant and oil of lubricating viscosity in the dispersed hydrated potassium borate composition.
Such additive packages can be added in effective amounts to an oil of lubricating viscosity to form a finished oil composition. Accordingly, the finished oil compositions of this invention contain the additive packages as described above upon further blending with an oil of lubricating viscosity. Preferably, the additive package described above, in an amount of from about 2 to 15 weight percent, is added to an oil of lubricating viscosity, in the amount of from about 85 to 98 weight percent, to provide for the finished gear oil composition wherein the weight percent of each component is based on the total weight of the composition. More preferably, added along with the oil of lubricating viscosity is a viscosity index improver which is included at a level of 0-12% and/or a pour point depressant at a level of 0-1%, to form a finished oil wherein the weight percent of each of the viscosity index improver and pour point depressant is based on the total weight of the composition.
In one of its method aspects, this invention is directed to a method for inhibiting gear damage, as measured by reduced wear and metal fatigue associated with ridging and pitting, during operation of a gear set at a temperature of at least 163xc2x0 C. which method comprises operating said gear set with a dispersed, hydrated, potassium borate composition comprising:
a hydrated potassium borate,
a dispersant,
optionally a detergent, and
an oil of lubricating viscosity
wherein the dispersed hydrated potassium borate composition is characterized by a hydroxyl:boron ratio (OH:B) of from at least 1.2:1 to 2.2:1, a potassium to boron ratio of from about 1:2.75 to 1:3.25 and a turbidity value of less than 300 ntu,.
When said gear set is operated at a temperature of 163xc2x0 C. over at least 8 hours, reduced gear damage, as measured by gear wear and pitting is observed.
This invention is also directed to a method for providing lower turbidity for dispersed hydrated potassium borate compositions which method comprises carefully controlling the hydroxyl:boron ratio (OH:B) of the dispersed hydrated potassium borate composition in the range of from at least 1.2:1 to 2.2:1, and preferably from about 1.3:1 to 2.1:1 and a potassium to boron ratio of from about 1:2.75 to 1:3.25.
This invention is still further directed to a method for the preparation of such dispersed hydrated potassium borate compositions which comprises:
mixing, under agitation, a mixture of an aqueous solution of boric acid and potassium hydroxide, where the stoichiometric ratio of the boric acid and the potassium hydroxide are selected to provide for a potassium to boron ratio in the product of from about 1:2.75 to 1:3.25, with an oil of lubricating viscosity and a dispersant, and then heating the mixture to remove sufficient water so as to produce a dispersed hydrated potassium borate composition having a OH:B ratio of from at least 1.2:1 to 2.2:1 and, preferably, from about 1.3:1 to about 2.1:1.
This invention is directed, in part, to novel dispersed hydrated potassium borate compositions comprising a hydrated potassium borate, a dispersant, optionally a detergent, and an oil of lubricating viscosity wherein said dispersed hydrated potassium borate composition is characterized by a hydroxyl:boron ratio (OH:B) of from at least 1.2:1 to 2.2:1, a potassium to boron ratio of from about 1:2.75 to 1:3.25 and a turbidity value of less than 300 ntu.
Each of these components in the claimed composition will be described in detail herein. However, prior to such a description, the following terms will first be defined.
The term xe2x80x9chydroxyl:boron ratioxe2x80x9d or xe2x80x9cOH:Bxe2x80x9d refers to a ratio of the number of hydroxyl groups attached to boron (moles of hydroxyl groups per mole of boron) in the dispersed hydrated potassium borate compositions as exemplified by, for example, structural formula I below. Another way to define the term xe2x80x9chydroxyl:boron ratioxe2x80x9d is to consider the formula:
K2O.xB2O3.yH2O
where x is between 2.75 and 3.25 and y is between 3.3 and 7.15, wherein the ratio of y to x is from at least 1.2:1 to 2.2:1, this ratio of y to x is the xe2x80x9chydroxyl:boron ratioxe2x80x9d. Preferably, this ratio is from about 1.3:1 to 2.1:1.
For the purposes of this application, the OH:B ratio of a dispersed hydrated potassium borate composition is calculated from the maximum infra-red (IR) absorbance between 3800 and 3250 cmxe2x88x921 (corrected by subtracting the baseline which is taken to be the absorbance at 3900 cm31 1) of a 5.000% solution, in a 0.215 mm transmittance cell, of the dispersed hydrated potassium borate composition in an oil of lubricating viscosity wherein all interfering absorbances due to other compounds or impurities have been subtracted. The remaining absorbance in this range corresponds to the hydroxyl groups of the dispersed hydrated potassium borate composition which is then converted to the OH:B ratio as follows:
OH:B=23.0Amax/%B
where Amax is the baseline corrected maximum IR absorbance (peak height)in the region 3800-3250 cmxe2x88x921; and
%B is the percent boron in the original (non-diluted) dispersed hydrated potassium borate composition sample.
The absorbance in this range, 3800 to 3250 cmxe2x88x921, corresponds to the hydroxyl groups of the potassium borate oligomer complex. If other additives are added to mask or interfere with the absorbance within this preferred range such groups will be subtracted from the IR spectra in the initial calculation of the OH:B ratio calculation.
In the examples below, this absorbance was measured with a Nicolet 5DXB FTIR Spectrometer fitted with a DTGS detector and CsI beam splitter. The spectrometer had CaF2 windows with 0.215 mm Teflon(copyright) spacer with small section cut out and a suitable cell holder. A spectrum of the sample was obtained using a 4 cmxe2x88x921 resolution.
The dispersed hydrated potassium borate composition preferably includes those compositions comprising from about 10 to 75 weight percent of the hydrated potassium borate; from about 2 to 40 weight percent of a dispersant; and from about 30 to 70 weight percent of an oil of lubricating viscosity, all based on the total weight of the composition. These compositions can be diluted to provide for an xe2x80x9cadditive packagexe2x80x9d as described above which, in turn, can be further diluted to provide for a fully formulated finished oil that is also described above.
Hydrated Potassium Borate
Hydrated potassium metal borates are well known in the art. Representative patents disclosing suitable borates and methods of manufacture include: U.S. Pat. Nos.3,313,727; 3,819,521; 3,853,772; 3,912,643; 3,997,454; and 4,089,790.1-6
These potassium metal borates can generally be represented by the following theoretical structural formula I:
where n is a number preferably from 1.0 to about 10.
In the compositions of this invention, the specific ratio of potassium to boron is limited to a range from about 1:2.75 to 1:3.25 and the specific ratio of hydroxyl to boron is from at least 1.2:1 to 2.2:1.
Dispersed alkali metal borate compositions comprising hydrated potassium metal borates are generally prepared by forming, in deionized water, a solution of potassium hydroxide and boric acid optionally in the presence of a small amount of potassium carbonate. The solution is then added to a lubricant composition comprising an oil of lubricating viscosity, a dispersant and any optional additives to be included therein (e.g., a detergent, sulfur containing compounds such as 2,2xe2x80x2-thiodiethanol, and the like, and other optional additives) to form an emulsion that is then dehydrated. Dehydration proceeds in three steps including an initial step of water removal that is initiated at a temperature of slightly over 100xc2x0 C. This initial step is followed by a slow increase in temperature whereupon the emulsion changes from turbid to clear. In the final step, there is a rapid increase in temperature and the liquid once again becomes turbid.
Formation of the hydrated potassium borates described herein is achieved by stoichiometric selection of the appropriate amounts of potassium hydroxide and boric acid and control of the extent of dehydration such that the resulting product has a ratio of potassium to boron in the range from about 1:2.75 to 1:3.25, a ratio of hydroxyl to boron of from at least 1.2:1 to 2.2:1, and a turbidity of less than 300 ntu.
In this invention, it was discovered that unexpected properties resulted when the degree of dehydration was carefully controlled to provide for a hydroxyl to boron ratio of from at least 1.2:1 to 2.2:1, and preferably from about 1.3:1 to 2.1:1. It was also discovered that unexpected properties resulted when the ratio of potassium to boron was carefully controlled to provide for a potassium to boron ratio of from about 1:2.75 to 1:3.25. Because of their retention of hydroxyl groups on the borate complex, these complexes are referred to as xe2x80x9chydrated potassium boratesxe2x80x9d and compositions containing oil/water emulsions of these hydrated potassium borates are referred to as xe2x80x9cdispersed hydrated potassium borate compositionsxe2x80x9d.
As stated above, the dehydration of the reaction mixture is closely monitored to ensure that the resulting dispersed hydrated potassium borate concentrate has a hydroxyl to boron ratio of from at least 1.2:1 to 2.2:1 when the reaction mixture is ultimately returned to a temperature of about 0xc2x0 C. to about 50xc2x0 C. and more preferably from about 20xc2x0 C. to 45xc2x0 C. In addition, related to a method aspect of the present invention, the dehydration procedure is carefully controlled (i.e., using a slower dehydration rate, employing a sweep gas, and the like) in order to avoid condensation of water on the walls of the reaction chamber. Condensation can result in water droplets in the lubricant composition which, in turn, may lead to undesired precipitate formation. Such precipitate formation typically results in large particles that must be filtered from the composition. Accordingly, in a preferred embodiment of this invention, dehydration occurs over a period of from about 1 to 10 hours, more preferably 3 to 8 hours. Optimization of the time, temperature and rate of air flow gives the preferred reaction design.
Preferred dispersed potassium borate compositions have a potassium-to-boron ratio of about 1:2.75 to 1:3.25 and more preferably 1:2.9 to about 1:3.1, and even more preferably about 1:3. In another of its preferred embodiments, the hydrated potassium borate particles generally have a mean particle size of less than 1 micron. In this regard, it has been found that the dispersed potassium borate compositions of this invention preferably have a particle size where 90% or greater of the particles are less than 0.6 microns.
In the dispersed hydrated potassium borate compositions, the hydrated potassium borates will generally comprise about 10 to 75 weight percent, preferably 25 to 50 weight percent, more preferably about 35 to 40 weight percent of the composition. (Unless otherwise stated, all percentages are in weight percent.)
Optionally, the dispersed potassium borate compositions contain small amounts of a water soluble oxo anion. Only from 0.001 moles to 0.11 moles of water soluble oxo anion should be present per mole of boron atom. This water-soluble oxo anion can include nitrate, sulfate, carbonate, phosphate, pyrophosphate, silicate, aluminate, germanate, stannate, zincate, plumbate, titanate, molybdate, tungstate, vanadate, niobate, tantalate, uranates, or can include the isopolymolybdates and isopolytungstates, or the heteropolymolybdates and heteropolytungstates, or mixtures thereof.
The presence of small amounts of water soluble oxo anions in the potassium borate lubricants is thought to improve the water tolerance of the potassium borates by disrupting the crystal structure of the hydrolysis products. This results in a lower tendency to form crystals or in a reduced rate of crystallization.
The additive packages and lubricant compositions of this invention can further employ surfactants, detergents, other dispersants and other conditions as described below and known to those skilled in the art. Optionally, the additive packages contain an alkylaromatic or polyisobutenyl sulfonate.
The dispersed hydrated potassium borate compositions of this invention generally comprise a dispersant, detergent and oil of lubricating viscosity that are further detailed below.
The Dispersant
The dispersant employed in the compositions of this invention can be ashless dispersants such as an alkenyl succinimide, an alkenyl succinic anhydride, an alkenyl succinate ester, and the like, or mixtures of such dispersants.
Ashless dispersants are broadly divided into several groups. One such group is directed to copolymers which contain a carboxylate ester with one or more additional polar function, including amine, amide, imine, imide, hydroxyl carboxyl, and the like. These products can be prepared by copolymerization of long chain alkyl acrylates or methacrylates with monomers of the above function. Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers, alkyl methacrylate-dialkylaminoethy methacrylate copolymers and the like. Additionally, high molecular weight amides and polyamides or esters and polyesters such as tetraethylene pentamine, polyvinyl polysterarates and other polystearamides may be employed. Preferred dispersants are N-substituted long chain alkenyl succinimides.
Alkenyl succinimides are usually derived from the reaction of alkenyl succinic acid or anhydride and alkylene polyamines. These compounds are generally considered to have the formula
wherein R1 is a substantially hydrocarbon radical having a molecular weight from about 400 to 3000, that is, R1 is a hydrocarbyl radical, preferably an alkenyl radical, containing about 30 to about 200 carbon atoms; Alk is an alkylene radical of 2 to 10, preferably 2 to 6, carbon atoms, R2, R3, and R4 are selected from a C1-C4 alkyl or alkoxy or hydrogen, preferably hydrogen, and x is an integer from 0 to 10, preferably 0 to 3. The actual reaction product of alkylene succinic acid or anhydride and alkylene polyamine will comprise the mixture of compounds including succinamic acids and succinimides. However, it is customary to designate this reaction product as a succinimide of the described formula, since this will be a principal component of the mixture. See, for example, U.S. Pat. Nos. 3,202,678; 3,024,237; and 3,172,892.
These N-substituted alkenyl succinimides can be prepared by reacting maleic anhydride with an olefinic hydrocarbon followed by reacting the resulting alkenyl succinic anhydride with the alkylene polyamine. The R1 radical of the above formula, that is, the alkenyl radical, is preferably derived from a polymer prepared from an olefin monomer containing from 2 to 5 carbon atoms. Thus, the alkenyl radical is obtained by polymerizing an olefin containing from 2 to 5 carbon atoms to form a hydrocarbon having a molecular weight ranging from about 400 to 3000. Such olefin monomers are exemplified by ethylene, propylene, 1-butene, 2-butene, isobutene, and mixtures thereof.
The preferred polyalkylene amines used to prepare the succinimides are of the formula:
wherein z is an integer of from 0 to 10 and Alk, R2, R3, and R4 are as defined above.
The alkylene amines include principally methylene amines, ethylene amines, butylene amines, propylene amines, pentylene amines, hexylene amines, heptylene amines, octylene amines, other polymethylene amines and also the cyclic and the higher homologs of such amines as piperazine and amino alkyl-substituted piperazines. They are exemplified specifically by ethylene diamine, triethylene tetraamine, propylene diamine, decamethyl diamine, octamethylene diamine, diheptamethylene triamine, tripropylene tetraamine, tetraethylene pentamine, trimethylene diamine, pentaethylene hexamine, ditrimethylene triamine, 2-heptyl-3-(2-aminopropyl)-imidazoline, 4-methyl imidazoline, N,N-dimethyl-1,3-propane diamine, 1,3-bis(2-aminoethyl)imidazoline,1-(2-aminopropyl)-piperazine, 1,4-bis(2-aminoethyl)piperazine and 2-methyl-1-(2-aminobutyl)piperazine. Higher homologs such as are obtained by condensing two or more of the above-illustrated alkylene amines likewise are useful.
The ethylene amines are especially useful. They are described in some detail under the heading xe2x80x9cEthylene Aminesxe2x80x9d in Encyclopedia of Chemical Technology, Kirk-Othmer, Vol. 5, pp. 898-905 (Interscience Publishers, New York, 1950).
The term xe2x80x9cethylene aminexe2x80x9d is used in a generic sense to denote a class of polyamines conforming for the most part to the structure
H2N(CH2CH2NH)aH
wherein a is an integer from 1 to 10.
Thus, it includes, for example, ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylene pentamine, pentaethylene hexamine, and the like.
Also included within the term xe2x80x9calkenyl succinimidesxe2x80x9d are post-treated succinimides such as post-treatment processes involving ethylene carbonate disclosed by Wollenberg, et al., U.S. Pat. No. 4,612,132; Wollenberg, et al., U.S. Pat. No. 4,746,446; and the like as well as other post-treatment processes each of which are incorporated herein by reference in its entirety.
Preferably, the polyalkylene succinimide component comprises from 2 to 40 weight percent, more preferably 5-20 weight percent, and even more preferably 10 to 15 weight percent, of the weight of the dispersed, hydrated potassium borate composition.
Polyalkylene succinic anhydrides or a non-nitrogen containing derivative of the polyalkylene succinic anhydride (such as succinic acids, Group I and/or Group II mono- or di-metal salts of succinic acids, succininate esters formed by the reaction of a polyalkylene succinic anhydride, acid chloride or other derivative with an alcohol, and the like) are also suitable dispersants for use in the compositions of this invention.
The polyalkylene succinic anhydride is preferably a polyisobutenyl succinic anhydride. In one preferred embodiment, the polyalkylene succinic anhydride is a polyisobutenyl succinic anhydride having a number average molecular weight of at least 500, more preferably at least 900 to about 3000 and still more preferably from at least about 900 to about 2300.
In another preferred embodiment, a mixture of polyalkylene succinic anhydrides is employed. In this embodiment, the mixture preferably comprises a low molecular weight polyalkylene succinic anhydride component and a high molecular weight polyalkylene succinic anhydride component. More preferably, the low molecular weight component has a number average molecular weight of from about 500 to below 1000 and the high molecular weight component has a number average molecular weight of from 1000 to about 3000. Still more preferably, both the low and high molecular weight components are polyisobutenyl succinic anhydrides.
Alternatively, various molecular weights polyalkylene succinic anhydride components can be combined as a dispersant as well as a mixture of the other above referenced dispersants as identified above.
As noted above, the polyalkylene succinic anhydride is the reaction product of a polyalkylene (preferably polyisobutene) with maleic anhydride. One can use conventional polyisobutene, or high methylvinylidene polyisobutene in the preparation of such polyalkylene succinic anhydrides. One can use thermal, chlorination, free radical, acid catalyzed, or any other process in this preparation.
Examples of suitable polyalkylene succinic anhydrides are thermal PIBSA (polyisobutenyl succinic anhydride) described in U.S. Pat. No. 3,361,673; chlorination PIBSA described in U.S. Pat. No. 3,172,892; a mixture of thermal and chlorination PIBSA described in U.S. Pat. No. 3,912,764; high succinic ratio PIBSA described in U.S. Pat. No. 4,234,435; PolyPIBSA described in U.S. Pat. Nos. 5,112,507 and 5,175,225; high succinic ratio PolyPIBSA described in U.S. Pat. Nos. 5,565,528 and 5,616,668; free radical PIBSA described in U.S. Pat. Nos. 5,286,799, 5,319,030, and 5,625,004; PIBSA made from high methylvinylidene polybutene described in U.S. Pat. Nos. 4,152,499, 5,137,978, and 5,137,980; high succinic ratio PIBSA made from high methylvinylidene polybutene described in European Patent Application Publication No. EP 355 895; terpolymer PIBSA described in U.S. Pat. No. 5,792,729; sulfonic acid PIBSA described in U.S. Pat. No. 5,777,025 and European Patent Application Publication No. EP 542 380; and purified PIBSA described in U.S. Pat. No. 5,523,417 and European Patent Application Publication No. EP 602 863. The disclosures of each of these documents are incorporated herein by reference in their entirety.
Preferably, the polyalkylene succinic anhydride component comprises from 2 to 40 weight percent, more preferably 5 to 20 weight percent, and even more preferably 10 to 15 weight percent, of the weight of the dispersed hydrated potassium borate composition.
Typically, in the dispersed hydrated potassium borate composition, the hydrated potassium borate is in a ratio of at least 2:1 relative to the polyalkylene succinic anhydride dispersant, while preferably being in the range of 2:1 to 10:1. In a more preferred embodiment the ratio is at least 5:2. In another preferred embodiment, mixtures as defined above of the polyalkylene succinic anhydrides are employed.
A particularly preferred combination of dispersants include a mixture of a polyalkylene succinic anhydride and a calcium polyisobutenyl sulfonate, especially those made from highly reactive polyisobutenes. Such mixtures are disclosed, for example, in U.S. patent application Ser. No. 09/967,049, filed on Sep. 28, 2001 and entitled xe2x80x9cLUBRICANT COMPOSITION COMPRISING ALKALI METAL BORATE DISPERSED IN A POLYALKYLENE SUCCINIC ANHYDRIDE AND A METAL SALT OF A POLYISOBUTENYL SULFONATExe2x80x9d, which application is incorporated herein by reference in its entirety.
The Detergent
The compositions of the present invention may optionally contain a detergent. There are a number of materials that are suitable as detergents for the purpose of this invention. These materials include phenates (high overbased or low overbased), high overbased phenate stearates, phenolates, salicylates, phosphonates, thiophosphonates and sulfonates and mixtures thereof. Preferably, sulfonates are used, such as high overbased sulfonates, low overbased sulfonates, or phenoxy sulfonates. In addition the sulfonic acids themselves can also be used.
The sulfonate detergent is preferably an alkali or alkaline earth metal salt of a hydrocarbyl sulfonic acid having from 15 to 200 carbons. Preferably the term xe2x80x9csulfonatexe2x80x9d encompasses the salts of sulfonic acid derived from petroleum products. Such acids are well known in the art. They can be obtained by treating petroleum products with sulfuric acid or sulfur trioxide. The acids thus obtained are known as petroleum sulfonic acids and the salts as petroleum sulfonates. Most of the petroleum products which become sulfonated contain an oil-solubilizing hydrocarbon group. Also included within the meaning of xe2x80x9csulfonatexe2x80x9d are the salts of sulfonic acids of synthetic alkyl aryl compounds. These acids also are prepared by treating an alkyl aryl compound with sulfuric acid or sulfur trioxide. At least one alkyl substituent of the aryl ring is an oil-solubilizing group, as discussed above. The acids thus obtained are known as alkyl aryl sulfonic acids and the salts as alkyl aryl sulfonates. The sulfonates where the alkyl is straight-chain are the well-known linear alkylaryl sulfonates.
The acids obtained by sulfonation are converted to the metal salts by neutralizing with a basic reacting alkali or alkaline earth metal compound to yield the Group I or Group II metal sulfonates. Generally, the acids are neutralized with an alkali metal base. Alkaline earth metal salts are obtained from the alkali metal salt by metathesis. Alternatively, the sulfonic acids can be neutralized directly with an alkaline earth metal base. The sulfonates can then be overbased, although, for purposes of this invention, overbasing is not necessary. Overbased materials and methods of preparing such materials are well known to those skilled in the art. See, for example, LeSuer U.S. Pat. No. 3,496,105, issued Feb. 17, 1970, particularly Cols. 3 and 4.
The sulfonates are present in the lubricating oil composition in the form of alkali and/or alkaline earth metal salts, or mixtures thereof. The alkali metals include lithium, sodium and potassium. The alkaline earth metals include magnesium, calcium and barium, of which the latter two are preferred.
Particularly preferred, however, because of their wide availability, are salts of the petroleum sulfonic acids, particularly the petroleum sulfonic acids which are obtained by sulfonating various hydrocarbon fractions such as lubricating oil fractions and extracts rich in aromatics which are obtained by extracting a hydrocarbon oil with a selective solvent, which extracts may, if desired, be alkylated before sulfonation by reacting them with olefins or alkyl chlorides by means of an alkylation catalyst; organic polysulfonic acids such as benzene disulfonic acid which may or may not be alkylated; and the like.
The preferred salts for use in the present invention are those of alkylated aromatic sulfonic acids in which the alkyl radical or radicals contain at least about 8 carbon atoms, for example from about 8 to 22 carbon atoms. Another preferred group of sulfonate starting materials are the aliphatic-substituted cyclic sulfonic acids in which the aliphatic substituents or substituents contain a total of at least 12 carbon atoms, such as the alkyl aryl sulfonic acids, alkyl cycloaliphatic sulfonic acids, the alkyl heterocyclic sulfonic acids and aliphatic sulfonic acids in which the aliphatic radical or radicals contain a total of at least 12 carbon atoms. Specific examples of these oil-soluble sulfonic acids include petroleum sulfonic acid, petrolatum sulfonic acids, mono- and poly-wax-substituted naphthalene sulfonic acids, substituted sulfonic acids, such as cetyl benzene sulfonic acids, cetyl phenyl sulfonic acids, and the like, aliphatic sulfonic acid, such as paraffin wax sulfonic acids, hydroxy-substituted paraffin wax sulfonic acids, etc., cycloaliphatic sulfonic acids, petroleum naphthalene sulfonic acids, cetyl cyclopentyl sulfonic acid, mono- and poly-wax-substituted cyclohexyl sulfonic acids, and the like. The term xe2x80x9cpetroleum sulfonic acidsxe2x80x9d is intended to cover all sulfonic acids that are derived directly from petroleum products.
Typical Group II metal sulfonates suitable for use in this composition include the metal sulfonates exemplified as follows: calcium white oil benzene sulfonate, barium white oil benzene sulfonate, magnesium white oil benzene sulfonate, calcium dipolypropene benzene sulfonate, barium dipolypropene benzene sulfonate, magnesium dipolypropene benzene sulfonate, calcium mahogany petroleum sulfonate, barium mahogany petroleum sulfonate, magnesium mahogany petroleum sulfonate, calcium triacontyl sulfonate, magnesium triacontyl sulfonate, calcium lauryl sulfonate, barium lauryl sulfonate, magnesium lauryl sulfonate, etc. The concentration of metal sulfonate that may be employed may vary over a wide range, depending upon the concentration of potassium borate particles. When present, however, the detergent concentration will generally range from 0.2 to about 10 weight percent and preferably from 3 to 7 weight percent. In addition, the compositions of this invention may contain a mixture of both a metal sulfonate and an ashless dispersant, as described above, where the ratio is a factor of achieving the proper stability of the hydrated, dispersed borate composition.
The Oil of Lubricating Viscosity
The lubricating oil to which the hydrated potassium borates and the dispersant are added can be any hydrocarbon-based lubricating oil or a synthetic base oil stock. Likewise, these lubricating oils can be added to the dispersed potassium borate compositions and additive packages containing them, as described herein, to form finished oil compositions. The hydrocarbon-based lubricating oils may be derived from synthetic or natural sources and may be paraffinic, naphthetic or asphaltenic base, or mixtures thereof. The diluent oil can be natural or synthetic, and can be different viscosity grades.
The lubricating oil comprises from 30 to 70 weight percent, more preferably from 45 to 55 weight percent, based on the total weight of the dispersed hydrated potassium borate composition.
Formulations
The dispersed hydrated potassium borate compositions of the present invention (as described herein above) are generally blended to form additive packages comprising such dispersed hydrated potassium borate compositions. These additive packages typically comprise from about 10 to 80 weight percent of the dispersed hydrated potassium borate composition described above and from about 90 to 20 weight percent of one or more of conventional additives selected from the group consisting of ashless dispersants (0-10%), detergents (0-5%), sulfurized hydrocarbons (0-40%), dialkyl hydrogen phosphates (0-15%), zinc dithiophosphates (0-20%), alkyl ammonium phosphates and/or thio- dithiophosphates (0-20%), phosphites (0-10%) pentaerythritol monooleate (0-10%), 2,5-dimercaptothiadiazole (0-5%), benzotriazole (0-5%), dispersed molybdenum disulfide (0-5%), foam inhibitors (0-2%), and imidazolines (0-10%) and the like wherein each weight percent is based on the total weight of the composition. It is understood, of course, that the addition of such conventional additives will dilute the concentration of the hydrated potassium borate, dispersant and oil of lubricating viscosity in the dispersed hydrated potassium borate composition.
Fully formulated finished oil compositions of this invention can be formulated from these additive packages upon further blending with an oil of lubricating viscosity. Preferably, the additive package described above is added to an oil of lubricating viscosity in an amount of from about 2 to 15 weight percent to provide for the finished oil composition wherein the weight percent of the additive package is based on the total weight of the composition. More preferably, added along with the oil of lubricating viscosity is a viscosity index improver which is included at a level of 0-12% and/or a pour point depressant at a level of 0-1%, to form a finished oil wherein the weight percent of each of the viscosity index improver and pour point depressant is based on the total weight of the composition.
A variety of other additives can be present in lubricating oils of the present invention. Those additives include antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure agents, antifoam agents, other viscosity index improvers, other anti-wear agents, and a variety of other well-known additives in the art.

Dispersed hydrated potassium borate compositions having improved properties in lubricating oil compositions


An oxide film is formed on a substrate by performing a cycle a predetermined number of times. The cycle includes: continuously performing supplying in advance an oxidant to a substrate in a process chamber and simultaneously supplying the oxidant and a precursor to the substrate in the process chamber, without having to purge an interior of the process chamber between the act of supplying in advance the oxidant and the act of simultaneously supplying the oxidant and the precursor; stopping the supply of the oxidant and the precursor to the substrate in the process chamber and purging the interior of the process chamber; and supplying the oxidant to the substrate in the purged process chamber.

As an example of processes of manufacturing a semiconductor device, a process of supplying a precursor containing a metal element and an oxidant to a substrate and forming an oxide film containing a metal element on the substrate is often carried out.
The present disclosure provides a technique capable of enhancing the productivity of a film forming process and improving a film quality when an oxide film containing a metal element is formed on a substrate using a precursor and an oxidant.

Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium


The present invention relates to a camera for a vehicle and a control method for the same and an exemplary embodiment of the present invention provides a camera for a vehicle which is provided in any one of a plurality of designated installation positions of the vehicle, including: an image sensor which generates a driving image; a receiving unit which receives a plurality of RF signals which are transmitted from a TPMS sensor unit which detects states of a plurality of tires included in the vehicle; and a position determining unit which determines which position among the plurality of installation positions is a position where the camera is installed, based on the plurality of RF signals which is received by the receiving unit.

Generally, when several cameras are installed in a vehicle, Ethernet cameras which have relatively simple interfaces are used and a plurality of Ethernet cameras is connected to an electronic control unit (ECU) through an Ethernet switch.
In this case, the ECU is connected to an upper link of the Ethernet switch to control the camera or receive image data from the camera while communicating with a plurality of cameras which is connected to a lower link of the Ethernet switch.
However, the camera for a vehicle of the related art has a drawback in that transmission of an image of the camera needs to be interrupted during a switching process which confirms a location of the camera or delay for stabilization occurs in every circuit when power is switched to determine the location of the camera. Further, similarly to the Ethernet network described above, when various application systems which are connected to one network share the same camera image resource, location information of the camera may not be shared.

Camera for vehicle and control method for the same


The present invention relates to a general purpose interface to a Fibre Channel array controller, more particularly to a gigabit interface converter (GBIC) or a gigabit link module (GLM) channel adapter, and to the use of a channel controller with associated general GBIC/GLM adapters to provide an ultra-high bandwidth bus. Specifically, the present invention provides an array controller. The array controller through programmable functionality causes a plurality of devices to appear as a single device. Moreover, the array controller provides a plurality of general purpose interfaces to allow connection of a plurality of heterogeneous devices. Thus, the present invention may allow an integrated storage system comprising disk drives, tape-units, CD-ROMs, optical drives, and/or the like. Alternatively, the array controller may be programmed to implement bus protocols. Thereby, the array controller may provide an ultra-high bandwidth bus by utilizing Fibre Channel connections and optical interfaces for connected devices.

The present invention relates to a general purpose interface to a Fibre Channel array controller, more particularly to a gigabit interface converter (GBIC) or a gigabit link module (GLM) channel adapter, and to the use of a channel controller with associated general GBIC/GLM adapters to provide an ultra-high bandwidth bus.
Enterprise resource planning systems and other sophisticated corporate data processing systems have gained substantial importance in recent years. Specifically, many corporate management theories posit that the success of an organization is directly related to the ability to gather and process enterprise information in an efficient and organized manner. To fulfill these goals, certain software companies have produced information management products such as RP/3 and the like. These types of software systems manage enormous amounts of information. Management of inventory levels, customer purchasing information, accounting data, employment information, and various other databases requires significant storage capacity. In addition, e-commerce has placed a premium upon transferring ordinary business operations to electronic work flows, thereby creating further storage capacity requirements. In addition, increased processing speed and capacity places greater demands upon storage resources.
Disk arrays have been designed to address these storage requirements. An exemplary disk array system is described in commonly assigned U.S. Pat. No. 5,392,244, entitled xe2x80x9cMEMORY SYSTEMS WITH DATA STORAGE REDUNDANCY MANAGEMENT,xe2x80x9d the disclosure of which is incorporated herein by reference. In essence, a disk array is a system that utilizes a number of discrete disks and interfaces with a host system or systems in such a manner that the assemblage of discrete disks appears as a single disk system. Disk arrays present numerous advantages. For example, disk arrays are highly redundant. If a particular discrete disk fails, the remaining portion of the disk array remains in operation. Moreover, disk arrays permit data mirroring, i.e. the same data may be stored upon more than one disk to provide greater redundancy against discrete disk failure. Accordingly, the probability of failure of the entire disk array is much lower than integrated storage systems.
Moreover, known disk array systems are designed to operate in a Fibre Channel environment. The Fibre Channel communication protocols are somewhat similar to the well-known Small Computer System Interface (SCSI) scheme, except for several differences. SCSI is a parallel interface standard used by various personal computers for attaching peripheral devices to computers. The Fibre Channel approach utilizes a mapped protocol to communicate frames, instead of individual bytes. Moreover, the Fibre Channel approach does not utilize parallel communication path connections. Instead, the Fibre Channel environments utilize serial communication channels to provide various system architectures, such as point-to-point, arbitrated loop, and crosspoint switched topologies. The serial communication approach simplifies system configuration. Specifically, the in-bound cable for one device in a Fibre Channel environment is the out-bound cable for a preceding device (either another independent unit or a fabric circuit switch). The fiber may comprise either an optical fiber cable or a twin-axial copper cable. For the remaining material, the term xe2x80x9cfiberxe2x80x9d shall be interchangeably utilized to mean either a fiber optical medium or a twin-axial copper cable. Also, it should be noted that Fibre Channel systems provide very high data communication rates. In fact, gigabit communication rates are possible. Fibre Channel systems rely upon intermediate devices to propagate information accurately between source and destination devices. Since the Fibre Channel architecture utilizes this approach, Fibre Channel systems limit the number of devices that may be present upon the system. This limitation is imposed to reduce latency and improve data communication rates.
Since there is an inherent limitation upon the number of devices present upon a Fibre Channel system, disk arrays operating upon a Fibre Channel system do not connect each individual disk unit to the external Fibre Channel system. Instead, a Fibre Channel disk array integrates the Fibre Channel in-bound and out-bound cables in a backplane. The Fibre Channel disk arrays further comprise a controller unit to arbitrate or manage communication between the discrete disk units and the Fibre Channel environment. The operating principles of an array controller is described in commonly assigned U.S. Pat. No. 5,471,640, entitled xe2x80x9cPROGRAMMABLE DISK ARRAY CONTROLLER HAVING N COUNTERS FOR N DISK DRIVES FOR STRIPPING DATA WHERE EACH COUNTER ADDRESSES SPECIFIC MEMORY LOCATION BY A COUNT OF N,xe2x80x9d the disclosure of which is incorporated herein by reference. The controller unit may provide a predetermined number of disk bays for connecting individual disk units. Thereby, the discrete disk units communicate directly with the controller unit. The controller unit assembles information received via the disk bays from the drives for communication in the forward direction over the fiber channel. Similarly, the controller unit separates data communicated in the reverse direction for distribution to the particular discrete drive units via appropriate disk bays. The controller unit further manages the discrete disk units in a manner that the plurality of units appears as a single disk. The controller unit implements mirroring tasks to provide for greater redundancy. Also, the use of Fibre Channel protocols permits efficient communication of data from discrete disk units to destination devices on the Fibre Channel system. Specifically, Fibre Channel protocols have demonstrated high bandwidth capability for large file transfers.
This architecture is quite useful to provide large storage capacity in an efficient and reliable fashion. However, the architecture of such disk array systems is specifically designed for a single purpose-data storage upon multiple discrete disk units. Moreover, the architecture provides very limited scalability. Specifically, the architecture limits the addition of discrete disk units to a predetermined number. At the present time, additional storage requirements must be fulfilled by providing a separate disk array system which obviously entails substantial expense. Also, the controller unit is singularly designed to interface with discrete disk units via the disk bays. Since the controller unit utilizes a specific interconnect, it is not possible to connect other devices via the disk bays.
The present invention provides an interface to facilitate a scalable and cost-effective disk array system. By doing so, the present invention simplifies operating system compatibility issues by facilitating scalable data storage. The present invention provides a general purpose interface to permit connection of heterogeneous devices to a Fibre Channel controller via plug-in connections. Also, the present invention facilitates connection of a plurality of heterogenous devices to a Fibre Channel system via a controller in a manner that the plurality of devices appears from a system perspective as a single device. Moreover, the present invention provides a general interface to a Fibre Channel controller to provide an ultra-high speed bus.
The present invention is directed to a general purpose interface to a Fibre Channel controller. The system provides a dual or greater slot interface to a single bay of a fiber channel system. The interface may preferably comprise two slots utilizing either a gigabit interface converter (GBIC) or a gigabit link module (GLM) for both slots. By providing a plurality of slots, the present invention permits scalable addition of devices to the Fibre Channel controller. The interface does not simply double the interface capacity of the Fibre Channel controller. Instead, individual interfaces may be serially connected. Thus, the interfaces permit exponential expansion of capacity to a single port of the Fibre Channel controller. Moreover, the present invention permits connection of heterogenous devices to the Fibre Channel controller in addition to discrete disk units. For example, the interface may permit connection of CD-ROM drives, tape units, networking cards, optical drives, and/or the like. In alternate embodiments, the present invention allows connection via other interfaces, such as SCSI interfaces, WDM interfaces, RS-232 interfaces, and/or the like.
Also, the present invention realizes that Fibre Channel controllers are not limited to disk array systems. By designing general purpose interfaces to a Fibre Channel controller, the present invention permits a Fibre Channel controller and its fiber channels to serve as an ultra-high speed bus. Specifically, any type of device may be connected to the controller. Thus, Fibre Channel controllers may provide the same capabilities of an ordinary bus with significantly higher bandwidth capability in accordance with the present invention.
The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and specific embodiment disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims. The novel features which are believed to be characteristic of the invention, both as to its organization and method of operation, together with further objects and advantages will be better understood from the following description when considered in connection with the accompanying figures. It is to be expressly understood, however, that each of the figures is provided for the purpose of illustration and description only and is not intended as a definition of the limits of the present invention.

Switch-on-the-fly GBIC disk channel adapter and disk channel system

Hewlett-Packard Development Company, L.P.


A method for distribution and transfer of entitlement certificates includes: storing account profiles, each account including an account identifier, primary account number, and account balance; receiving an entitlement request from a computing device including a specific account identifier, entitlement balance, and usage controls; identifying a specific account profile that includes the specific account identifier; generating an entitlement certificate that includes the entitlement balance and usage controls; generating an entitlement identifier for the entitlement certificate; placing a hold associated with the entitlement certificate on the account balance included in the specific account profile for the entitlement balance; and transmitting the entitlement certificate to the computing device.

As the security and variety of available payment instruments increases, consumers have grown more and more accustomed to making purchases with transaction accounts via associated payment instruments in place of cash. Payment instruments offer greater convenience and security than cash does, as there is often only a single card or device that need be carried, and if the payment instrument is lost or stolen the consumer may be able to recover the instrument or receive a replacement without losing their money. As such, many consumers often prefer the use of payment instruments in place of cash.
However, there are instances where payment instruments may be less convenient than cash. For example, a person-to-person transfer of funds may be difficult, and in some instances impossible, to perform using traditional payment instruments. In addition, traditional payment instruments often require a working connection between the merchant or individual receiving a payment instrument and a payment network or financial institution associated therewith for processing the transaction. Furthermore, payment via a payment instrument may not be guaranteed for a merchant, as the funds may never end up being transferred to the merchant due to intermediate actions taken by the consumer. As such, there are instances where the use of cash may be beneficial over a payment instrument associated with a transaction account.
Thus, there is a need for an improved technological system where a payment instrument may be suitable for use in making guaranteed payments, person-to-person payments, and payments for transactions in instances where a recipient may lack a connection to a payment network or other payment processor. Such technological improvements may increase the utility of payment instruments to accommodate for some of the traditional advantages gained via cash purchases.

Method and system for distribution, use and validation of electronic entitlement certificates


A method of screening a continuous tone image into a halftone representation for a flexographic printing operation can compensate for characteristic printing problems in highlight areas by selectively placing non-printing dots or pixels proximate highlight dots. The non-printing dots or pixels raise the printing relief floor in the highlight areas providing additional support for marginally printable image features.

Flexographic printing is a method of direct rotary printing that uses a resilient relief image in a plate of rubber or photopolymer to print articles such as cartons, bags, labels or books. Flexographic printing has found particular application in packaging, where it has displaced rotogravure and offset lithography printing techniques in many cases. While the quality of articles printed using flexographic plates has improved significantly as the technology has matured, physical limitations related to the process of creating a relief image in a plate remain.
In particular, it is very difficult to print small graphic elements such as fine dots, lines and even text using flexographic printing plates. In the lightest areas of the image (commonly referred to as highlights) the density of the image is represented by the total area of dots in a halftone screen representation of a continuous tone image. For Amplitude Modulated (AM) screening, this involves shrinking a plurality of halftone dots located on a fixed periodic grid to a very small size, the density of the highlight being represented by the area of the dots. For Frequency Modulated (FM) screening, the size of the halftone dots is generally maintained at some fixed value, and the number of randomly or pseudo-randomly placed dots represent the density of the image. In both the aforementioned cases, it is necessary to print very small dot sizes to adequately represent the highlight areas.
Maintaining small dots on a flexographic plate is very difficult due to the nature of the plate making process. Digital flexographic plate precursors have an integral UV-opaque mask layer coated over the photopolymer. In a pre-imaging (or post-imaging) step the floor of the plate is set by area exposure to UV light from the back of the plate. This exposure hardens the photopolymer to the relief depth required for optimal printing. This step is followed by selective ablation of the mask layer with an imagewise addressable high power laser to form an image mask that is opaque to ultraviolet (UV) light in non-ablated areas. Flood exposure to image-forming UV radiation and chemical processing follow wherein the areas not exposed to UV are removed in a processing apparatus using solvents or by a heating and wicking process. The combination of the mask and UV exposure produces relief dots that have a generally conical shape. The smallest of these dots are prone to being removed during processing, which means no ink is transferred to these areas during printing (the dot is not "held" or formed on plate and/or on press). Alternatively, if the dot survives processing they are susceptible to damage on press. For example small dots often fold over and/or partially break off during printing causing either excess ink or no ink to be transferred.
Conventional or non-digital flexographic platemaking follows a similar process except that the integral mask is replaced by a separate film mask or phototool that is imaged separately and placed in contact with the photopolymer plate precursor under a vacuum frame for the image-forming UV exposure.
In printing, it is well known that there is a limit to the minimum size of halftone dot that may be reliably represented on a plate and subsequently printed on press. The actual minimum size will vary with a variety of factors including plate type, ink, imaging device characteristics etc. This creates a problem in the highlight areas when using conventional AM screening since once the minimum dot size is reached, further size reductions will generally have unpredictable results. If, for example, the minimum size dot that can be printed is a 50×50 μm square dot, corresponding to a 5% tone at 114 lines per inch screen frequency, then it becomes very difficult to faithfully reproduce tones between 0% and 5%. A common workaround is to increase the highlight values in the original file to ensure that after imaging and processing, that all the tonal values in the file are reproduced as printing dots and are properly formed on the plate. However, the downside to this practice is the additional dot gain in the highlights, which causes a noticeable transition between inked and non-inked areas. Another well-known practical way of improving highlights is through the use of "Respi" or "double dot" screening. One such technique is shown in FIG'S. 1-A to 1-C. A screening grid 10 for conventional AM screen is shown in a simplified schematic format. The screening grid comprises a plurality of halftone cells 12. A halftone cell is an area wherein an AM halftone dot is grown from a low density, where only a small dot is placed at the centre of the cell, to a high density or solid where the cell is completely filled. In FIG. 1-A, dots 14 are placed only in every second halftone cell. Dots 14 have size corresponding to the minimum reliably reproducible dot. As the density of the screen is increased, dots 14 are increased in size as shown in FIG. 1-B at 16. At some point in increasing the density, the previously empty halftone cells are populated with minimum size dots 18 as shown in FIG. 1-C. The dots 16 may be held at a fixed size with increasing screen density while allowing dots 18 to grow. When all dots are the same size as dots 16, conventional AM screening takes over.
The problem with this type of screening technique when applied to flexographic printing is that the size of dot that may be printed in isolation is actually quite large, typically 40-50 μm in diameter. Even when using this technique, the highlights are difficult to reproduce without having a grainy appearance (which occurs when dots are spaced far apart to represent a very low density) and the printed dot may also suffer an undesirable dot gain.
There remains a need to improve the representation of small dots in flexographic printing processes.

This patent is subject to a terminal disclaimer.

Kodak Graphic Communications Canada Company


The display apparatus includes an image display element being driven based on a digital video signal, a quantizing part converting an input analog image signal into the digital video signal based on a quantization phase and a quantization frequency, and a converting part converting an input value into an output value, the input value being a difference value of signal values of pixels adjacent to each other in the digital video signal. The apparatus includes an accumulating part accumulating the output values from the converting part that converts the difference values obtained over entire pixels in one frame of the digital video signal to produce an accumulation evaluation value, and a controller adjusting the quantization phase in the quantizing part such that the accumulation evaluation value becomes maximum. The output values a(m) for the input values k1, k2 and k3 satisfy conditions of a(k1+1)−a(k1)<a(k2+1)−a(k2), a(k2+1)−a(k2)=a(k3+1)−a(k3) and k1<mi-1≦k2<k3<mi.

1. Field of the Invention
The present invention relates to a display apparatus such as a projector and a television monitor.
2. Description of the Related Art
When displaying analog video signals for documents and graphics produced by a computer on a display apparatus, it is important to match a quantization clock and an effective image area, which are needed to quantize the analog video signal in the computer, with those in the display apparatus. In order to perform proper quantization, it is necessary to optimize a frequency of the quantization clock (hereinafter referred to as a "quantization frequency") and a phase of the quantization clock (hereinafter referred to as a "quantization phase"), and thus a function of automatically performing such optimization, which is a so-called automatic quantization clock adjustment function, has been proposed.
Japanese Patent Laid-Open No. 11-177847 discloses an apparatus having such an automatic quantization clock adjustment function. This apparatus performs for each phase a process to acquire an accumulated value of differences between video signal values of one or more pairs of pixels adjacent to each other in one frame of an input video signal. As shown in FIG. 6, since proper quantization increases the accumulated value of the video signal value differences and improper quantization decreases the accumulated value, the apparatus adjusts the quantization frequency and quantization phase such that the acquired accumulated value of the video signal value differences becomes maximum.
Moreover, Japanese Patent Laid-Open No. 2000-020008 discloses an apparatus having an automatic quantization clock adjustment function that accumulates, in order to acquire the accumulated value described in Japanese Patent Laid-Open No. 11-177847, square values of the video signal value differences.
The apparatus disclosed in Japanese Patent Laid-Open No. 11-177847 is based on a premise that, as shown in FIG. 6, the input video signal includes some parts where an inclination of video signal level change reverses at each pixel, and improves adjustment accuracy of the automatic quantization clock adjustment function as such parts increases. However, for an input video signal including no or few parts where the inclination of the video signal level change reverses at each pixel, the accumulated value of the video signal value differences in the proper quantization and that in the improper quantization have no difference, as shown in FIG. 7, which makes it impossible to perform sufficient adjustment.
Moreover, the apparatus disclosed in Japanese Patent Laid-Open No. 2000-020008 includes a large scale circuit for calculation of the square value, which increases cost.


An electronic device can include an organic active layer and an electrode. In one aspect, the electrode can further include a first layer that is conductive, and a second layer that is conductive. The second layer can include a defect extending at least partly through a thickness of the second conductive layer. The electrode can also include a third layer lying within and substantially filling the defect, wherein each of the second and third layers includes a same metallic element.

1. Field of the Disclosure
The invention relates generally to electronic devices and, more specifically, to electronic devices including organic active materials and processes for forming the same.
2. Description of the Related Art
Electronic devices, including organic electronic devices, continue to be more extensively used in everyday life. Examples of an organic electronic device can include an Organic Light-Emitting Diode ("OLED"). A low work function material can be used as a part of an electrode of the OLED. An example of a low work function material can be a Group 1 or Group 2 metal, or any combination thereof. Such a material can react with moisture if not properly sealed. Such a reaction can render the electronic device unusable.
One approach to fabricating an electrode with a low work function can be to form the electrode with two layers. A first layer of the electrode containing the low work function material can be closer to an organic active layer of the device, and a second layer of the electrode acts as a conductor and helps prevent the first layer from contacting moisture.
Radiation at a targeted wavelength or in a targeted spectrum may need to pass through the electrode in a particular application. However, if radiation at a targeted wavelength or in a targeted spectrum is to pass through the electrode using the two-layer approach, the second layer of the electrode may not have a sufficient thickness to prevent moisture from reaching the first layer of the electrode. A defect extending at least partly through the second layer may cause premature failure of the electronic device.

Electronic device including an organic active layer and process for forming the electronic device

Abstract: In another aspect, a process for forming an electronic device can include forming an organic active layer and forming a first layer that is conductive and is part of an electrode. The process can also include forming a second layer and exposing the second layer to a first plasma to form a first compound from the second layer.


System and method for producing tree perspectives of a plurality of storage systems using storage system descriptors and a set of search rules. The system and method herein provide an easy way to locate and identify specific storage systems. The storage system descriptors comprise external storage system metadata (referred to herein as “external metadata”) and/or internal storage system attributes (referred to herein as “internal attributes”) that describe the storage systems. The set of search rules comprises one or more metadata search rules and/or one or more attribute search rules. The set of search rules may be applied to the external metadata and/or internal attributes to determine a set of one or more matching storage systems. A tree perspective may be produced that represents the set of matching storage systems. The tree perspective may display the hierarchal organization of the set of matching storage systems through a hierarchical tree structure.

A storage system typically comprises one or more storage devices for storing client data. The storage system includes a storage operating system that functionally organizes the system by, inter alia, invoking storage operations in support of a storage service implemented by the system. The storage system may be implemented in accordance with a variety of storage architectures including, but not limited to, a network-attached storage environment, a storage area network and a disk assembly directly attached to a client or host computer. For example, the storage devices may be organized as a storage array. In some embodiments, a storage device may comprise a disk device commonly described as a self-contained rotating magnetic media storage device, such as a hard disk drive (HDD) or direct access storage device (DASD). In other embodiments, a storage device may comprise another type of storage device.
The storage operating system of the storage system may implement a high-level module, such as a file system, to logically organize the information stored on volumes as a hierarchical structure of storage objects, such as files and logical units (LUs). A known type of file system is a write-anywhere file system that does not overwrite data on disks. An example of a write-anywhere file system that is configured to operate on a storage system is the Write Anywhere File Layout (WAFL®) file system available from NetApp, Inc. Sunnyvale, Calif.
The storage system may be further configured to allow many servers to access storage objects stored on the storage system. In this model, the server may execute an application, such as a database application, that "connects" to the storage system over a computer network, such as a point-to-point link, shared local area network (LAN), wide area network (WAN), or virtual private network (VPN) implemented over a public network such as the Internet. Each server may request the data services of the storage system by issuing access requests (read/write requests) as file-based and block-based protocol messages (in the form of packets) to the system over the network.
A plurality of storage systems may be interconnected to provide a cluster architecture configured to service many servers. The storage systems of the cluster may be configured to communicate with one another to act collectively to increase performance or to offset any single storage system failure within the cluster. The cluster provides data service to servers by providing access to a shared storage (comprising a set of storage devices). Typically, servers will connect with a storage system of the cluster for data-access sessions with the storage system. During a data-access session with a storage system, a server may submit access requests (read/write requests) that are received and performed by the storage system.
A manager server may be used to manage a large number of storage systems for performing maintenance, monitoring, or other management functions on the storage systems. Currently, a simple list of the storage systems may be used to identify a specific storage system. However, when managing an increasingly large number of storage systems, it becomes more difficult to identify a specific storage system or identify faulty storage systems needing attention using the current simple lists. For example, a manager server may manage hundreds or thousands of storage systems, and an administrator would typically need to analyze the entire list of storage systems to identify specific storage systems. As such, there is a need for a better method of managing and identifying storage systems for allowing an administrator to manage a large number of storage systems.

System and method for producing tree perspectives of storage systems


The grocery cart cup holder a front, middle, and rear frame. The front frame has along an outer end a plurality of front clips, which are used to secure the front frame onto the shopping cart seat frame. The middle frame has at least one circular opening, and is hingedly connected to both the front frame and rear frame. The rear frame has at least one back clip that attaches onto the shopping cart seat frame. The grocery cart cup holder can fold flat to enable use of the grocery cart seat, and the cup holder can fold up to provide a cup holder that consists of the circular opening at an elevated position working in tandem with the grocery cart seat to create a cup holder.

A. Field of the Invention
The present invention relates to the field of cup holders, more specifically, a portable cup holder system that works in conjunction with a grocery cart.
A typical grocery cart has a main protrusion for placing groceries therein as well as a seat, which folds out along a side closest to where the handle is located. The seat can fold out and provide a place for holding personal items, such as a handbag or purse, or to support a small child, as in the intended use. When the seat is not being used, the frame can fold up and rearwards to lay flat against a rear wall of the shopping cart.
When shopping there is a need to provide a cup holder such that the shopper may place his or her beverage safety upon said grocery cart without the fear of spilling. The present invention can simply snap upon the shopping cart seat frame, and of which can fold flat when not in use to enable the seat to be used or for the frame to fold flat, or wherein the cup holder frame can fold out to for a cup holder that provides a place to rest at least one cup thereon.
B. Discussion of the Prior Art
As a preliminary note, it should be stated that there is an ample amount of prior art that deals with portable cup holder systems. As will be discussed immediately below, no prior art discloses a foldable storable shopping cart beverage cup holder that clips onto the shopping cart seat, and of which folds flat when not in use so as to not impede use of the seat, and of which folds out to provide at least one cup holder thereon.
The Werner Patent (U.S. Pat. No. 6,749,204) discloses a beverage cup holder for a shopping cart. However, the cup holder is permanently affixed to the shopping cart as opposed to a portable cup holder that clips onto the shopping cart seat, and of which folds out to form a cup holder or that can fold away flat when not in use in order to retain function of the shopping cart seat.
The Adamson et al. Patent (U.S. Pat. No. 5,494,306) discloses an adjustable cup holder for a shopping cart. However, the adjustable cup holder attaches to the handle of the shopping cart as opposed to the shopping cart seat.
The Bergin et al. Patent (U.S. Pat. No. 5,938,091) discloses a cup holder that is mountable on the interior of a supermarket cart and which includes flanges that can be used for directly mounting the cup holder to the cart wall. However, the cup holder attaches onto a wall of the shopping cart as opposed to the shopping cart seat, and of which does not further fold flat when not in use or fold out to provide at least one cup holder when in use.
The Azzarelli et al. Patent (U.S. Pat. No. 5,531,238) discloses a walker caddy container having a cup holder. However, the cup holder is directed to use with a walker caddy and not a shopping cart seat.
The Southerland Patent (U.S. Pat. No. 5,494,308) discloses a shopping cart storage device. However, the storage device hangs from an exterior brace of a shopping cart seat, provides no cup holder thereon, and does not fold flat when not in use.
The Lines Patent (U.S. Pat. No. Des. 383,284) illustrates a design for a shopping cart cup holder, which does not depict a body capable of attaching to the seat of a shopping cart or the ability to fold flat.
While the above-described devices fulfill their respective and particular objects and requirements, they do not describe a foldable storable shopping cart beverage cup holder that clips onto the shopping cart seat, and of which folds flat when not in use so as to not impede use of the seat, and of which folds out to provide at least one cup holder thereon. In this regard, the grocery cart cup holder departs from the conventional concepts and designs of the prior art.


Provided herein is aerogel insulating material and a method of producing aerogel insulating material, the aerogel insulating material including an insulating layer containing aerogel particles, a adhesive-coating layer located at both surfaces of the insulating layer, and a lamination film surrounding the adhesive-coating layer, wherein the adhesive-coating layer has thermoplastic elastomer having a low glass transition temperature. The method of producing aerogel insulating material includes preparing (S10), coating (S20), drying (S30), cutting (S40), and laminating (S50).

1. Field of the Invention
The following description relates to an aerogel insulating material and manufacturing method thereof, and more particularly to an aerogel insulating material consisting of an insulating layer containing aerogel particles; an adhesive-coating layer containing an inorganic solvent, thermoplastic elastomer and additive on both surfaces of the insulating layer; and a lamination film. The thermoplastic elastomer of the adhesive-coating layer may be made of ethylenevinyl acetate copolymer or polyurethane having a low glass transition temperature, and through this characteristic, it is possible to strengthen the adhesive and embody an insulating material insulating structure having excellent durability and low migration rate of the aerogel particles.
2. Description of Related Art
Aerogel is a compound word of air meaning air and gel meaning solidified liquid. Aerogel consists of silicon oxide (SiO2) threads each of which is 1/10,000 thick of a strand of hair sparsely tangled. Between each silicon oxide thread, there are air molecules which take up 98% of the total volume. The density of aerogel is approximately 0.003 g/m3, that is, 3 times the air density (0.001 g/m3), the lightest solid on earth.
The diameter of a hole in the aerogel is smaller than the average transition distance of an air particle, and thus the aerogel airtight, thereby effectively preventing heat conduction. The heat conductivity of the aerogel is so low that even when placed on a palm of a hand and fire flames of 1,000° C. or above are placed close to the palm, heat is not conducted very well. Furthermore, an advantage of aerogel is that it has a high intensity that even when an automobile is placed on top of 4 aerogels each having the size of a palm of a hand, the aerogel would not break. Hence, it is suitable as insulating material. Therefore, there are various application fields for aerogel, for examine, clothing and industrial insulating material etc.
When applying such aerogel to products, aerogel particles must be put inside capsules to prevent them from migration. For example, aerogel particles migrated from insulating material such as clothing are rather rough and thus may easily irritate human skin tissues, which is a problem. Several methods have been used for application in products, but conventional aerogel particles easily migrate, lack resistance against mechanical washing and drying, and are ineffective in insulating.
Accordingly, it is desirable to develop a technology which could prevent easy migration of aerogel particles when using products containing aerogel, thereby maintaining the low heat conductivity and low weight characteristics of the aerogel.

Insulating material containing aerogel and method for preparing the same

Abstract: Therefore, according to the present disclosure, it is possible to embody aerogel insulating material for use in clothing and which may reduce migration of aerogel particles, and which may make the most of the advantage of aerogel, such as its light weight and the excellent insulating effect.


An agent for capturing metal ions, which consists essentially of a cyclic inulooligosaccharide having from 6 to 8 molecules of fructose bonded by .beta.-2,1 bonds to form a cyclic structure, wherein hydroxyl groups may all or partially be alkylated.

1. Field of the Invention
The present invention relates to a novel agent for capturing metal ions consisting essentially of a specific cyclic inulooligosaccharide.
2. Discussion of Background
Heretofore, many methods have been proposed for separating and removing metal ions from various compounds or mixtures. As a typical example, there is a method of capturing and recovering metal ions in a solution by means of a chelate compound. Further, a method of recovering metal ions by means of cyclodextrin known to form a clathrate compound, or a method of employing various crown ethers, is also well known.
The method for capturing metal ions by means of a chelate compound had a problem that it was difficult to properly select a chelate compound suitable for the metal ions to be captured, since the capturing performance depends on various factors including the types of the metal ion and the ligand forming the chelate compound and the size of the chelate ring.
In the case of the capturing and recovering method by means of cyclodextrin, cyclodextrin has in its molecule a hydrophobic space by virtue of its specific molecular structure and takes into the space various compounds in an aqueous solution to form a clathrate compound, whereby guest molecules having higher hydrophobic nature tend to be more readily taken into the space. Accordingly, there has been a problem that ions having low hydrophobic nature can not be captured by such cyclodextrin. Further, there has been a problem that cyclodextrin is hardly soluble in water.
The method of employing crown ethers has problems such that crown ethers are insoluble in water, and they are highly toxic to human bodies.
Further, these conventional metal ion capturing agents are all expensive, and their applicable ranges are rather limited.


A digital to analog converting system, which comprises: a first data converting circuit, for receiving a first digital data stream transmitted at a first clock frequency, for converting the first digital data stream to a plurality of second digital data streams transmitted at a second clock frequency, and for outputting the second digital data streams in parallel; a second data converting circuit, for receiving the second digital data streams from the first data converting circuit, and for converting the second digital data streams to a third digital data stream transmitted at a third clock frequency; and a first digital to analog converter, for converting the third digital data stream to a first output analog data stream. The second clock frequency is lower than the first clock frequency and the third clock frequency.

For a transmitter in a communication system, a DAC (digital to analog converter) with a filter is always required. For different communication systems, a DAC may operate at different sampling rates and the filter may need different corners. In a wide-band system, the DAC may operate at a high sampling rate. However, the high-speed interface for transmitting data to the DAC cannot be precisely predicted. Also, the speed of the interface may be limited due to the loading and the DAC cannot reach the high-speed sampling rate.

Digital to analog converting system and digital to analog converting method


There is provided mechanisms for beamforming. A method is performed by a network node. The network node is capable of communicating with served wireless devices using multiple beams generated by analog beamforming in an antenna array. The method comprises identifying, based on statistics of handovers of the served wireless devices between the beams, a need to combine at least two of the beams into a new beam. The method comprises determining beamforming weights to be applied at the analog antenna array for generating the new beam. The method comprises communicating with the served wireless devices using the new beam with the determined beamforming weights having been applied at the analog antenna array.

In communications networks, there may be a challenge to obtain good performance and capacity for a given communications protocol, its parameters and the physical environment in which the communications network is deployed.
For example, transmission schemes and reception schemes based on the use of narrow beams might be needed at high frequencies to compensate for propagation losses. For a given communication link, a beam can be applied at both the network side (such as at the transmission and reception point (TRP) of a network node) and the user side (such as at wireless devices served by the network node). A beam pair link (BPL) is defined by the beam used by the TRP (denoted TRP beam) for communicating with the wireless device and the beam used by the wireless device (denoted WD beam) for communicating with the TRY. Each of the TRP beam and the WD beam could be used for any of transmission and reception. Likewise, there could be separate BPLs for downlink communications (Where the TRP beam is a transmission (TX) beam and where the WD beam is a reception (RX) beam) and uplink communications (where the TRP beam is an RX beam and where the WD beam is a TX beam).
In general terms, a beam management procedure is used to discover and maintain BPLs. A BPL is expected to be discovered and monitored by the network using measurements on downlink reference signals used for beam management, such as channel state information reference signals (CSI-RS). The CSI-RS for beam management can be transmitted periodically, semi-persistently or aperiodic (such as being event triggered) and they can be either shared between multiple wireless devices or be device-specific. In order to find a suitable TRP beam the TRP transmits CSI-RS in different TRP TX beams on which the wireless devices performs reference signal received power (RSRP) measurements and reports back the N best TRP TX beams (where the value of N can be configured by the network). Furthermore, the CSI-RS transmission on a given TRP TX beam can be repeated to allow the wireless device to evaluate suitable WD beams, thus enabling so-called WD RX beam training.
The wireless devices and/or the transmission and reception point (TRP) of the network node could implement beamforming by means of analog beamforming, digital beamforming, or hybrid beamforming. Each implementation has its advantages and disadvantages. A digital beamforming implementation is the most flexible implementation of the three but also the costliest due to the large number of required radio chains and baseband chains. An analog beamforming implementation is the least flexible but cheaper to manufacture due to a reduced number of radio chains and baseband chains compared to the digital beamforming implementation. A hybrid beamforming implementation is a compromise between the analog and the digital beamforming implementations. As the skilled person understands, depending on cost and performance requirements of different wireless devices, different implementations will be needed.
One drawback with an analog beamforming implementation is that the TRP only can transmit or receive in one beam at a time (assuming one antenna array being active at the time, and the same beam being used for both polarizations, which usually is the case in order to counteract dropped signal strength due to polarization mismatching).
For served wireless devices with high mobility, beam management may require significant amount of overhead signalling due to the fact that the serving beam has to be updated frequently, thus resulting in a high number of handovers between different beams at one and the same TRP. This overhead is extra severe when the TRP is using analog beamforming, due to the fact that only one TRP beam then can be used at each time instance, which for example makes TRP beam sweeping (needed to find the new TRP beam) costlier.
Hence, there is still a need for improved beam management.


The present invention relates to a method for detection of film mode or camera mode of a video sequence. This detection is carried out using histograms of video levels of frames of the video sequence. Difference histograms are calculated then compared with each other so as to generate difference parameters for each video frame of the sequence. The pattern formed by these difference parameters is then compared with predetermined patterns to deduce the mode, film or camera, of the sequence. The advantage of this method is that it requires just small memory resources for its implementation and can therefore be implanted in an FPGA circuit.

The detection of film mode is traditionally used in modern televisions to determine the processes to apply to images received with a view to improving their display quality. Among these processes, it is notably known to convert the frame sequence received into a frame sequence having a higher frequency to suppress the flicker effect that appears on the television screen when the frequency of frames displayed is less than 60 Hz. To do this, in the case of an input frequency at 50 Hz, it is known in the art to double the frame frequency and carry it at 100 Hz. This frequency change consists for example in duplicating the frames of the input sequence, as shown in FIG. 1. In this example, the sequence to be converted, noted as ABC, comprises three frames. The first frame represents image A, the second frame represents image B and the third frame represents image C. The duplication operation consists in transforming this sequence of three frames into a sequence of 6 frames, AABBCC, having a double frequency. The two first frames of the transformed sequence are identical and represent the image A. In the same way, the two following frames represent the image B and the two last frames represent the image C. This duplication operation results in suppressing the flicker effect during the displaying of the new sequence but however creates a judder effect when the displayed images comprise motion.
To eliminate this judder effect, it is known in the prior art to compensate the movement of added frames as shown in FIG. 2. In the example illustrate by this figure, the frame representing image A in the input sequence is converted, in the output sequence, into a frame representing image A and a frame representing a motion compensated image A′. To generate image A′, the motion is estimated between image A and the next image, which is image B, and an intermediary image is created A′ based on the motion estimated between these two images. In the same way, the frame representing image B is converted, in the output sequence, into a frame representing the image B and a frame representing a motion compensated image B′ and the frame representing image C is converted, in the output sequence, into a frame representing the image C and a frame representing a motion compensated image C′. This increase in frequency with motion compensation enables suppressing the flicker effect while conserving a fluidity of motion in the sequence.
This type of processing (augmentation of the frequency with or without motion compensation) is however only valid when the input sequence does not comprise duplicated frames, for example when the sequence is in film format (24 or 25 images per second) or in camera format (50 or 60 images per second).
In particular this processing is not applicable when an input sequence, of film format (24 or 25 images per second) origin, has been transformed into a telecine stream by a format conversion of 2:2 pull-down conversion type or a 3:2 pull-down conversion type with a view to its display on a television (50 or 60 images per second). The 2:2 pull-down conversion is used to pass from 25 images per second (film format) to 50 images per second (PAL/SECAM format). This conversion consists in duplicating each input frame. The 3:2 pull-down conversion is used to pass from 24 images per second (film format) to 60 images per second (NTSC format). Each pair of consecutive input frames is then converted into 5 output frames, the three first output frames being identical to the first input frame of the pair and the two other output frames being identical to the second input frame of the pair. In the remainder of the description, reference is made to a video frames sequence in film mode to designate this type of video frames sequence, that originally was in film mode and was converted with a view to its display on a screen and that now comprises duplicated frames, and video frames sequence in video mode or camera mode designates a sequence of video frames in camera format that does not comprise duplicated frames.
With regard to what has preceded, it is easily understood that, for a sequence in film mode (comprising duplicated frames), the processing applied to reduce the flicker creates a great deal of judder when the frames of the sequence in film mode are simply duplicated (without motion compensation) as there is then duplication of already duplicated frames. This judder problem is also present when added frames are motion compensated because, for some among them, the motion estimation is carried out between two identical frames, one being the duplicate of the other. The motion estimation is then null and the motion compensation of no use.
It is therefore important to detect the mode, film or camera, in the sequence of frames to be processed before applying any processing, such as, for example, that described previously to reduce the flicker effect. It can also be of interest to determine the type of film mode of the sequence (film mode 2:2 or film mode 3:2) and identify in the sequence, the frames corresponding to the frames of the original sequence in film format (24 or 25 images per second) between which a motion estimation and a motion compensation can be viably carried out.
Methods for detection of film mode are known in the prior art. All of these methods are based either on a motion estimation, or on Displaced Frame Difference (DFD) and require the complete storage of at least one video frame. When the detection of film mode is carried out by a programmable circuit of FPGA (Field Programmable Gate Array) type, it is then necessary to add an external memory to the FPGA circuit to store said video frame.

Method for detection of film mode or camera mode