EP2300553A2 - Système de transfert thermique, fluide, et procédé - Google Patents

Système de transfert thermique, fluide, et procédé

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Publication number
EP2300553A2
EP2300553A2 EP09795240A EP09795240A EP2300553A2 EP 2300553 A2 EP2300553 A2 EP 2300553A2 EP 09795240 A EP09795240 A EP 09795240A EP 09795240 A EP09795240 A EP 09795240A EP 2300553 A2 EP2300553 A2 EP 2300553A2
Authority
EP
European Patent Office
Prior art keywords
heat transfer
transfer fluid
combination
magnesium
fluid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09795240A
Other languages
German (de)
English (en)
Other versions
EP2300553A4 (fr
Inventor
Bo Yang
Filipe J. Marinho
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Prestone Products Corp USA
Original Assignee
Honeywell International Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Honeywell International Inc filed Critical Honeywell International Inc
Publication of EP2300553A2 publication Critical patent/EP2300553A2/fr
Publication of EP2300553A4 publication Critical patent/EP2300553A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/10—Liquid materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/173—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition

Definitions

  • This disclosure generally relates to a heat transfer system, heat transfer fluid, and heat transfer method.
  • a heat transfer system in communication with the power source, regulates the generated heat, and ensure that the power source operates at an optimum temperature.
  • the heat transfer system generally comprises a heat transfer fluid that facilitates absorbing and dissipating the heat from the power source.
  • Heat transfer fluids which generally comprise water and a glycol, are in intimate contact with one or several metallic parts that are prone to corrosion. Thus, several corrosion inhibitors are added to the heat transfer fluid in order to protect the metallic parts from corrosion.
  • Traditional heat transfer fluids can exhibit extremely high conductivities, often in the range of 3000 microsiemens per centimeter ( ⁇ S/cm) or more.
  • This high conductivity produces adverse effects on the heat transfer system by promoting corrosion of metal parts, and also in the case of power sources where the heat transfer system is exposed to an electrical current, such as in fuels cells or the like, the high conductivity can lead to short circuiting of the electrical current and to electrical shock.
  • Aluminum, magnesium, and their alloys are increasingly used in the manufacture of several components of a heat transfer system. They are advantageous due to their light weight, high strength, and relative ease of manufacture, among others.
  • Aluminum, magnesium, and their alloys can be used in heat transfer systems of internal combustion engines and alternative power sources.
  • magnesium, aluminum, and their alloys are highly susceptible to corrosion when in contact with traditional heat transfer fluids with high conductivity.
  • the foaming of traditional heat transfer fluids further contributes to the corrosion of aluminum, magnesium, and their alloys. Therefore, a need exists for heat transfer systems and fluids intended for use therein, wherein the heat transfer systems comprise aluminum, magnesium, or their alloys, in intimate contact with the heat transfer fluid.
  • the heat transfer fluids advantageously have low conductivity and good foaming properties.
  • a heat transfer system comprising a circulation loop defining a flow path for a heat transfer fluid, and a heat transfer fluid comprising a liquid coolant, a siloxane corrosion inhibitor of formula R 3 -Si- [0-Si(R) 2 ]X-OSiR 3 , wherein R is independently an alkyl group or a polyalkylene oxide copolymer of 1 to 200 carbons, x is from 0 to 100, and further wherein at least one alkyl group and at least one polyalkylene oxide copolymer are present, and a non-conductive po Iy diorgano siloxane antifoam agent, wherein the conductivity of the heat transfer fluid is less than about 100 ⁇ S/cm, and wherein the heat transfer system comprises aluminum, magnesium, or a combination thereof, in intimate contact with the heat transfer fluid.
  • a heat transfer fluid comprises a liquid coolant, a siloxane corrosion inhibitor of formula R 3 -Si-[O-Si(R) 2 ] X -OSiR 3 , wherein R is independently an alkyl group or a polyalkylene oxide copolymer of 1 to 200 carbons, x is from 0 to 100, and further wherein at least one alkyl group and at least one polyalkylene oxide copolymer are present, and a non-conductive poly diorgano siloxane antifoam agent, wherein the conductivity of the heat transfer fluid is less than about 100 ⁇ S/cm.
  • a heat transfer method comprises contacting a heat transfer system with a heat transfer fluid, wherein the heat transfer system comprises a circulation loop defining a flow path for the heat transfer fluid, and aluminum, magnesium, or a combination thereof, wherein the heat transfer fluid comprises a liquid coolant, a siloxane corrosion inhibitor of formula R 3 -Si-[O-Si(R) 2 ] ⁇ -OSiR 3 , wherein R is independently an alkyl group or a polyalkylene oxide copolymer of 1 to 200 carbons, x is from 0 to 100, and further wherein at least one alkyl group and at least one polyalkylene oxide copolymer are present, and a non-conductive polydiorganosiloxane antifoam agent, wherein the conductivity of the heat transfer fluid is less than about 100 ⁇ S/cm, and wherein the aluminum, magnesium, or combination thereof is in intimate contact with the heat transfer fluid.
  • FIG. 1 is a schematic diagram of one embodiment of the heat transfer system
  • FIG. 2 is a schematic diagram of another embodiment of the heat transfer system.
  • a heat transfer fluid comprising a liquid coolant, a siloxane corrosion inhibitor, and a non-conductive polydiorganosiloxane antifoam agent
  • a heat transfer fluid is an effective low conductivity heat transfer fluid that is advantageous for use in heat transfer systems where the heat transfer fluid is in intimate contact with aluminum, magnesium, or their alloys, and/or with power sources where the heat transfer fluid is exposed to an electrical current.
  • the conductivity of the heat transfer fluid is advantageously less than about 100 ⁇ S/cm.
  • the heat transfer fluid further comprises an azole.
  • aluminum refers to aluminum metal, alloys thereof, or a combination thereof
  • magnesium refers to magnesium metal, alloys thereof, or a combination thereof
  • the liquid coolant comprises an alcohol, water, or a combination of an alcohol and water. It is advantageous to use deionized water, demineralized water, or a combination thereof, which generally exhibit a conductivity lower than that of water which has not been deionized or demineralized.
  • the heat transfer fluid can be a concentrated heat transfer fluid, that is, a heat transfer fluid comprising a liquid coolant consisting essentially of alcohols. Concentrated heat transfer fluids are advantageous for storage and shipping. Concentrated heat transfer fluids can, if desired, be combined with water prior to or after use in the heat transfer system.
  • the heat transfer fluid can, on the other hand, be a diluted heat transfer fluid, that is, a heat transfer fluid comprising alcohols and water. Both concentrated and diluted heat transfer fluids are suitable for use in the heat transfer system.
  • the heat transfer fluid comprises a concentrated heat transfer fluid.
  • the heat transfer fluid comprises a diluted heat transfer fluid.
  • Water can be present in the heat transfer fluid in an amount of about 0.01 to about
  • water can be present in the heat transfer fluid in an amount of about 0.5 to about 70 wt%, and more specifically about 1 to about 60 wt%, based on the total weight of the heat transfer fluid.
  • the heat transfer fluid can be free of water.
  • the alcohol comprises monohydric alcohols, polyhydric alcohols, or mixtures of monohydric and polyhydric alcohols.
  • monohydric alcohols include methanol, ethanol, propanol, butanol, furfural, tetrahydrofurfurol, ethoxylated furfural, alkoxy alkanols such as methoxyethanol, and the like, and combinations comprising at least one of the foregoing monohydric alcohols.
  • Non-limiting examples of polyhydric alcohols include, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- propylene glycol, 1,3-propylene glycol (or 1,3-propanediol), dipropylene glycol, butylene glycol, glycerol, glycerol- 1,2-dimethyl ether, glycerol- 1,3-dimethyl ether, monoethylether of glycerol, sorbitol, 1,2,6-hexanetriol, trimethylol propane, and the like, and combinations comprising at least one of the foregoing polyhydric alcohols.
  • the alcohol can be present in the heat transfer fluid in an amount of about 10 to about 99.9 wt%, based on the total weight of the heat transfer fluid. Specifically, the alcohol can be present in the heat transfer fluid in an amount of about 30 to about 99.5 wt%, and more specifically about 40 to about 99 wt%, based on the total weight of the heat transfer fluid.
  • Siloxane corrosion inhibitors comprise polysiloxanes or organosilane compounds comprising a silicon-carbon bond, or combinations thereof.
  • Suitable polysiloxanes are those of the formula R3-Si-[O-Si(R)2] x -OSiR3 wherein R is independently an alkyl group or a polyalkylene oxide copolymer of 1 to 200 carbons and x is from 0 to 100, more specifically 2 to 90, more specifically 3 to 80, more specifically 4 to 70, and even more specifically 5 to 60.
  • the siloxane corrosion inhibitors comprise polysiloxanes or organosilane compounds comprising a silicon-carbon bond, or a combination thereof, and further comprising at least one group that is a polyalkylene oxide copolymer of one or more alkylene oxides having from 2 to 6 carbons, specifically from 2 to 4 carbons.
  • the siloxane corrosion inhibitor is of the formula R 3 -Si-[O-Si(R) 2 ] x -OSiR 3 wherein R is independently an alkyl group or a polyalkylene oxide copolymer of 1 to 200 carbons and x is as discussed above, and further wherein at least one alkyl group and at least one polyalkylene oxide copolymer.
  • Non-limiting examples of commercially available polysiloxanes for use herein include the SILWET siloxanes from GE Silicones/OSi Specialties, and other similar silo xane-po Iy ether copolymers available from Dow Corning or other suppliers.
  • siloxane corrosion inhibitors comprise SILWET L-77, SILWET L-7657, SILWET L-7650, SILWET L-7600, SILWET L-7200, SILWET L-7210 or the like.
  • Organosilane compounds comprise a silicon-carbon bond capable of hydro lyzing in the presence of water to form a silanol, that is, a compound comprising silicon hydroxide.
  • Organosilane compounds can be of the formula R 5 Si(OZ) 3 wherein R' and Z are independently an aromatic group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkenyl group, and can comprise a heteroatom such as N, O, or the like, in the form of functional groups such as amino groups, epoxy groups, or the like.
  • R' is an aromatic group, an alkyl group, a cycloalkyl group, an alkoxy group, or an alkenyl group, and can comprise a heteroatom such as N, O, or the like, in the form of functional groups such as amino groups, epoxy groups, or the like, and Z is a C1-C5 alkyl group.
  • Non-limiting examples of commercially available organosilane compounds for use herein include the SILQUEST and FORMASIL surfactants from GE Silicones/OSi Specialties, and other suppliers.
  • siloxane corrosion inhibitors comprise FORMASIL 891, FORMASIL 593, FORMASIL 433, SILQUEST Y- 5560 (polyalkyleneoxidealkoxysilane), SILQUEST A-186 (2-(3,4- epoxycyclohexyl)ethyltrimethoxysilane), SILQUEST A-187 (3- glycidoxypropyltrimethoxysilane), or other SILQUEST organosilane compounds available from GE Silicones, Osi Specialties or other suppliers and the like.
  • Non-limiting examples of other organosilane compounds for use herein include 3- aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, octyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and those organosilane compounds having a structure similar to the foregoing, but varying numbers of carbon atoms.
  • the siloxane corrosion inhibitor can be present in the heat transfer fluid in an amount of about 0.01 to about 10 wt%, more specifically about 0.02 to about 2 wt%, based on the total weight of the heat transfer fluid.
  • the non-conductive po Iy diorgano siloxane antifoam agents comprise any po Iy diorgano siloxane antifoam agents.
  • the non-conductive poly diorgano siloxane antifoam agents are those where the terminal groups at the molecular chain are selected from a trimethylsilyl group, a dimethylhydroxysilyl group, and a combination thereof.
  • the polydiorganosiloxane is polydimethylsiloxane.
  • the polydimethylsiloxanes for use herein has the formula (CH 3 )3SiO-(SiCH3)2 ⁇ ) m -Si(CH 3 )3, where m is from 1 to 30,000.
  • the po Iy diorgano silo xanes have a kinematic viscosity of about 5 to about 100 million mm 2 /sec at 25 0 C. More specifically, the kinematic viscosity of the polydimethylsiloxanes is about 10 to about 1,000,000 mni 2 /sec at 25 0 C and the average molecular weight is about 1000 to about 200,000 Daltons.
  • Polydiorganosiloxanes for use herein also include polydiethylsiloxanes, polydimethyl polydiphenyl siloxane copolymers, polydimethyl-poly(chloropropyl methyl)siloxanes, and a combination thereof.
  • G comprises an alkyleneoxide or a polyoxyalkylene group.
  • G include oxyalkylene groups having the formula -(CH 2 ) z (OCH 2 CH 2 ) m OH, -(CH 2 ) z (OCH 2 CH 2 CH 2 ) m OH, -(CH 2 ) z O(OCH 2 CH 2 ) m H, -(CH 2 ) z O(OCH 2 CH 2 CH 2 ) m H,
  • the polydiorganosiloxane antifoam agent can further comprise up to about 20 wt% of a finely divided filler.
  • a finely divided filler include fumed, precipated, and plasmatic TiO 2 , Al 2 O 3 , Al 2 O 3 /SiO 2 , ZrO 2 /SiO 2 , and SiO 2 .
  • Hydrocarbon waxes, triglycerides, long chain fatty alcohols, fatty acid esters and finely divided polyolef ⁇ n polymers, such as polypropylene, polyisobutylene, are additional examples of fillers for use herein.
  • the finely divided filler can be hydrophilic or hydrophobic.
  • the filler can be hydrophobed during manufacturing of the antifoam or independently.
  • Various grades of silica having a particle size of several nanometers to several microns and a specific surface area of about 40 to about 1000 m 2 /g, more specifically a specific surface area of about 50 to about 400 m 2 /g, are commercially available and suitable for use as the filler in the polydiorganosiloxane based antifoams.
  • hydrophobized silica having a specific surface area of about 50 to about 350 m 2 /g is used as the filler.
  • Non-limiting examples of silica fillers for use herein include AEROSIL R 812, and R 812S from Evonik Degussa (Essen,
  • TULLANOX 503 and 1080 from Tulco (MA, U.S.A.), and similar products from other suppliers.
  • the polydiorganosiloxane antifoam agent can further comprise up to 20 wt% of a hydrophobic oil.
  • a hydrophobic oil include mineral oil, hydrocarbon oils derived from carbonaceous sources, such as petroleum, shale, and coal, and equivalents thereof.
  • Mineral oils include heavy white mineral oil which is high in paraffin content, light white mineral oil, petroleum oils such as aliphatic or wax-base oils, aromatic and asphalt-base oils, mixed-base oils, petroleum derived oils such as lubricants, engine oils, machine oils, and cutting oils, and medicinal oils such as refined paraffin oil.
  • the mineral oils are available commercially from several suppliers, including, but not limited to, Exxon Company (Houston, TX), and Shell Chemical Company (Houston, TX).
  • the polydiorganosiloxane antifoam agent can further comprise other components, such as polyalkylenoxide, water, alkylene glycol, surfactants, antiseptic agents, and biocides, up to about 95 wt%.
  • Non-limiting examples of commercially available non-conductive polydimethylsiloxane based antifoam agents and emulsions thereof include PC-5450NF from Performance Chemicals LLC, XD-55 and XD-56 from CNC International, and Y- 14865 from Momentive Performance Materials.
  • the non-conductive polydiorganosiloxane antifoam agent can be present in the heat transfer fluid in an amount of about 1 to about 3000 parts per million (ppm), specifically about 100 to about 2000 ppm, more specifically about 200 to about 1000 ppm, based on the total weight of the heat transfer fluid.
  • the heat transfer fluid further comprises an azole.
  • Azoles for use herein include f ⁇ ve-membered heterocyclic compounds having 1 to
  • Non-limiting examples of azoles include pyrroles, pyrazoles, imidazoles, triazoles, thiazoles and tetrazoles according to formulas (I)-(IV):
  • R 1 and R 2 are independently a hydrogen atom, a halogen atom such, a Ci_2o alkyl or cycloalkyl group, SR 3 , OR 3 , or NR 3 2 , wherein R 3 is independently a hydrogen atom, a halogen atom, or a Ci_2o alkyl or cycloalkyl group, X is independently N or CR 2 , and Y is independently N or CR 1 .
  • Non-limiting examples of azoles include pyrrole, methylpyrrole, pyrazole, dimethyl pyrazole, benzotriazole, tolyltriazole, methyl benzotriazole such as 4-methyl benzotriazole and 5-methyl benzotriazole, butyl benzotriazole, mercaptobenzothiazole, benzimidazole, halo -benzotriazole such as chloro-methylbenzotriazole, tetrazole, methyl tetrazole, mercapto tetrazole, thiazole, 2-mercaptobenzothiazole and the like.
  • the azole comprises benzotriazole, tolyltriazole, mercaptobenzothiazole, or a combination thereof. In one exemplary embodiment, the azole comprises benzotriazole. In another exemplary embodiment, the azole comprises tolyltriazole.
  • the azole can be present in the heat transfer fluid in an amount of 0.0001 to about 10 wt%, specifically about 0.01 to about 8 wt%, more specifically about 0.5 to about 4 wt%, based on the total weight of the heat transfer fluid.
  • the heat transfer fluid can further comprise additional corrosion inhibitors that are non- ionic.
  • additional corrosion inhibitors include fatty acid esters, such as sorbitan fatty acid esters, polyalkylene glycols, polyalkylene glycol esters, copolymers of ethylene oxide and propylene oxide, polyoxyalkylene derivatives of sorbitan fatty acid esters, or the like, or combinations thereof.
  • the average molecular weight of additional corrosion inhibitors is from about 55 to about 300,000 daltons, and more specifically from about 110 to about 10,000 daltons.
  • Non- limiting examples of sorbitan fatty acid esters include sorbitan monolaureates such as SPAN 20, ARLACEL 20, or S-MAZ 20Ml, sorbitan monopalmitates such as SPAN 40 or ARLACEL 40, sorbitan monostearates such as SPAN 60, ARLACEL 60, or S-MAZ 6OK, sorbitan mono-oleate such as SPAN 80 or ARLACEL 80, sorbitan monosesquioleate such as SPAN 83 or ARLACEL 83, sorbitan trioleate such as SPAN 85 or ARLACEL 85, sorbitan tristearate such as S-MAZ 65K, sorbitan monotallate such as S-MAZ 90, or the like, or combinations thereof.
  • sorbitan monolaureates such as SPAN 20, ARLACEL 20, or S-MAZ 20Ml
  • sorbitan monopalmitates such as SPAN 40 or ARLACEL 40
  • Non-limiting examples of polyalkylene glycols include polyethylene gycols, polypropylene glycols, and combinations thereof.
  • Non-limiting examples of polyethylene glycols for use herein include those available commercially under the tradename CARBOWAX polyethylene gycols and methoxypolyethylene glycols from Dow Chemical Company, such as CARBOWAX PEG 200, 300, 400, 600, 900, 100, 1450, 3350, 4000, or 8000, under the trademark PURACOL polyethylene glycols from BASF Corporation, such as PURACOL E 200, 300, 400, 600, 900, 1000, 1450, 3350, 4000, 6000, or 8000.
  • Non-limiting examples of polyalkylene glycol esters include mono- or di-esters of various fatty acids, such as those available under the tradename MAPEG polyethylene glycol esters from BASF Corporation, such as MAPEG 200ML or PEG 200 Monolaureate, MAPEG 400 DO or PEG 400 Dioleate, MAPEG 400 MO or PEG 400 Mono-oleate, and MAPEG 500 DO or PEG 600 Dioleate.
  • Non-limiting examples of copolymers of ethylene oxide and propylene oxide include various PLURONIC and PLURONIC R block copolymer surfactants such as those available under the trademark DOWFAX non-ionic surfactants, UNCON(RO) fluids and SYNALOX lubricants from DOW Chemical.
  • Non-limiting examples of polyoxyalkylene derivatives of a sorbitan fatty acid ester include polyoxy ethylene 20 sorbitan monolaurate available under the tradename TWEEN 20 or T-MAZ 20, polyoxy ethylene 4 sorbitan monolaurate available under the tradename TWEEN 21, polyoxy ethylene 20 sorbitan monopalmitate available under the tradename TWEEN 40, polyoxy ethylene 20 sorbitan monostearate available under the tradenames TWEEN 60 and T-MAZ 6OK, polyoxy ethylene 20 sorbitan mono-oleate available under the tradename TWEEN 80 or T-MAZ 80, polyoxy ethylene 20 tristearate available under the tradename TWEEN 65 or T-MAZ 65K, polyoxyethylene 5 sorbitan mono-oleate available under the tradename TWEEN 81 or T-MAZ 81, polyoxyethylene 20 sorbitan trioleate available under the tradename TWEEN 85 or T-MAZ 85K, and the like.
  • the heat transfer fluid can further comprise colloidal silica.
  • Colloidal silica for use herein is of an average particle size of about 1 nanometer (nm) to about 200 nm, more specifically from about 1 nm to about 100 nm, and even more specifically from about 1 nm to about 40 nm.
  • the colloidal silica is advantageous as a secondary corrosion inhibitor, and can sometimes improve the heat transfer properties of the heat transfer fluid. While not wishing to be bound by theory, it is believed that the use of silica of a particular average particle size provides improvements in heat transfer efficiency and/or heat capacity by providing a large surface area for contact with the liquid coolant.
  • colloidal silica examples include LUDOX from DuPont or Grace Davidson, NYACOL or BINDZIL from Akzo Nobel or Eka Chemicals, SNOWTEX from Nissan Chemical.
  • Other suppliers of suitable colloidal silica include Nalco and the like.
  • the colloidal silica can be present in the heat transfer fluid in an amount of 0.01 to about 10,000 ppm, more specifically of about 0.02 to about 2000 ppm, and even more specifically about 0.1 to about 1000 ppm, based on the total weight of the heat transfer fluid.
  • additional corrosion inhibitors include cyclohexanoic carboxylates derived from long chain fatty acids, as well as salts and esters thereof, and amine compounds, such as mono-, di-, and triethanolamine, morpholine, benzylamine, cyclohexylamine, dicyclohexylamine, hexylamine, 2-amino-2-methyl-l-propanol, diethylethanolamine, diethylhydroxylamine, 2-dimethylaminoethanol, dimethylamino-2-propanol, and 3- methoxypropylamine.
  • These additional corrosion inhibitors can be added to the heat transfer fluid, with the proviso that they do not produce adverse effects.
  • the other additional corrosion inhibitors can be present in the heat transfer fluid in an amount of
  • the heat transfer fluid comprises a tetraalkylort ho silicate ester.
  • the tetraalkylortho silicate ester comprises a Ci- C20 alkyl group, non-limiting examples of which include tetramethylorthosilicate, tetraethylorthosilicate, and the like.
  • the tetraalkylorthosilicate ester can be present in the heat transfer fluid in an amount of 0.01 wt% to about 5 wt%, based on the total weight of the heat transfer fluid.
  • the corrosion inhibiting heat transfer fluid can further comprise a non-conductive colorant that is a non-ionic or a weakly ionic species soluble or dispersible in the liquid coolant at the concentration of the colorant required to provide coloring of the heat transfer fluid.
  • the non-conductive colorant is substantially free of functional groups that will form an ionic species due to hydrolysis in an aqueous alcohol or alkylene glycol solution.
  • the non-conductive colorant is substantially free of functional groups selected from the group consisting of carboxylate groups, sulfonate groups, phosphonate groups, quaternary amines, groups that carry a positive charge, and groups that carry a negative charge.
  • Non-limiting examples of groups that carry a positive charge include Na + , Cu 2+ , -NRV where R 3 is H, C1-C20 alkyl groups or aromatic ring containing groups, Fe 3+ , the like, and combinations thereof.
  • Non-limiting examples of groups that carry a negative charge include Cl “ , Br “ , I “ , and the like, and combinations thereof.
  • Non-limiting examples of non-conductive colorants include a chromophore such as anthraquinone, triphenylmethane, diphenylmethane, azo containing compounds, diazo containing compounds, triazo containing compounds, xanthene, acridine, indene, phthalocyanine, azaannulene, nitroso, nitro, diary lmethane, triarylmethane, methine, indamine, azine, oxazine, thiazine, quinoline, indigoid, indophenol, lactone, aminoketone, hydroxyketone, stilbene, thiazole, a conjugated aromatic groups, a conjugated heterocyclic group (e.g., stilbene, bis-triazenylaminostilbene, pyrazoline, and/or coumarin type molecule or a combination thereof), a conjugated carbon-carbon double bond (e.g., carotene), and
  • the non-conductive colorants will comprise a diarylmethane, triarylmethane, triphenylmethane, diphenylmethane, a conjugated aromatic group, an azo group, or a combination thereof.
  • the non-conductive colorant comprises a chromophore comprising a conjugated aromatic group.
  • the non-conductive colorant can comprise alkyleneoxy or alkoxy groups and a chromophore such as described above.
  • the chromophore is selected from the group consisting of anthraquinone, triphenylmethane, diphenylmethane, azo containing compounds, diazo containing compounds, triazo containing compounds, compounds comprising one or more conjugated aromatic groups, one or more conjugated heterocyclic groups, and combinations thereof.
  • non-conductive colorants can be of the formula
  • R 4 ⁇ Ak[(E) n R 5 ] m ⁇ y
  • R 4 is an organic chromophore selected from the group consisting of anthraquinone, triphenylmethane, diphenylmethane, azo containing compounds, diazo containing compounds, triazo containing compounds, xanthene, acridine, indene, thiazole, compounds comprising one or more conjugated aromatic groups, one or more conjugated heterocyclic groups, or combinations thereof
  • A is a linking moiety and is selected from the group consisting of O, N or S
  • k is 0 or 1
  • E is selected from the group consisting of one or more Ci-Cs alkyleneoxy or alkoxy groups
  • n is 1 to 100
  • m is 1 or 2
  • y is 1 to 5
  • R 5 is selected from the group consisting of H, Ci- Ce alkyl or Ci-Cs alkoxy groups, or combinations thereof.
  • the non-conductive colorants are of the formula R 4 ⁇ A k [(E) n R 5 ] m ⁇ y wherein R 4 is as described above, A is N or O, k is 0 or 1, E is a C 2 -C 4 alkyleneoxy group, n is from 1 to 30, m is 1 or 2, y is 1 or 2, and R 5 is H, a C1-C4 alkyl group, or a Ci-C 6 alkoxy group.
  • the non-conductive colorants can be prepared by various known methods such as those described in U.S. Patent No. 4,284,729, U.S. Patent No. 6,528,564 or other patents issued to Milliken & Company, Spartanburg, SC, USA.
  • suitable colorants can be prepared by converting a dyestuff intermediate containing a primary amino group into the corresponding polymeric compound and employing the resulting compound to produce a compound having a chromophoric group in the molecule.
  • azo dyestuffs this can be accomplished by reacting a primary aromatic amine with an appropriate amount of an alkylene oxide or mixtures of alkylene oxides, such as ethylene oxide and the like, according to known procedures, and then coupling the resulting compound with a diazonium salt of an aromatic amine.
  • colorants containing contaminating ionic species can be used if purification methods are employed. Illustrative purification and chemical separation techniques include treatment with ion exchange resins, reverse osmosis, extraction, absorption, distillation, filtration, and the like, and similar processes used to remove the ionic species and obtain a purified colorant that is electrically non-conductive.
  • Non-limiting examples of commercially available non-conductive colorants for use in the heat transfer fluid include LIQUITINT Red ST or other similar polymeric colorants from Milliken Chemical of Spartanburg, SC, USA, or colorants from
  • Chromatech of Canton, MI, USA Illustrative examples include the following:
  • LIQUITINT Red ST LIQUITINT Blue RE
  • LIQUITINT Red XC LIQUITINT Patent
  • LIQUITINT Yellow BL LIQUITINT Yellow II
  • LIQUITINT Sunbeam Yellow LIQUITINT Sunbeam Yellow
  • LIQUITINT Red BL LIQUITINT Red RL
  • LIQUITINT Cherry Red LIQUITINT Red II
  • LIQUITINT Teal LIQUITINT Yellow LP
  • LIQUITINT Violet LS LIQUITINT
  • the non-conductive colorant is selected from the group consisting of LIQUITINT Red ST from Milliken, LIQUITINT Red XC from Chromatech, CHROMATINT Yellow 1382 from Chromatech and LIQUITINT Blue®
  • the non-conductive colorant is LIQUITINT Blue RE from Chromatech.
  • the non-conductive colorant can be present in the heat transfer fluid in an amount of 0.0001 to 0.2 wt%, based on the total weight of the heat transfer fluid. In another embodiment, the non-conductive colorant can be present in the heat transfer fluid in an amount of 0.0002 to 0.1 wt%, based on the total weight of the heat transfer fluid, while in one exemplary embodiment, the non-conductive colorant can be present in an amount of 0.0003 to 0.05 wt%, based on the total weight of the heat transfer fluid.
  • the heat transfer fluids can also comprise additional additives such as other colorants, wetting agents, other antifoam agents, biocides, bitterants, nonionic dispersants or combinations thereof in amounts of up to 10 wt%, based on the total weight of the heat transfer fluid.
  • additional additives such as other colorants, wetting agents, other antifoam agents, biocides, bitterants, nonionic dispersants or combinations thereof in amounts of up to 10 wt%, based on the total weight of the heat transfer fluid.
  • the conductivity of the heat transfer fluid can be measured by using the test methods described in ASTM Dl 125, that is, "Standard Test Methods for Electrical
  • the conductivity of the heat transfer fluid disclosed herein is less than about 100 ⁇ S/cm. In one embodiment, the conductivity is less than about 70 ⁇ S/cm, while in another embodiment, the conductivity is less than about 50 ⁇ S/cm, and yet in another embodiment the conductivity is less than about 25 ⁇ S/cm.
  • the heat transfer fluid can have an electrical conductivity of about 0.02 to about 100 ⁇ S/cm, specifically about 0.02 to about 50 ⁇ S/cm, more specifically about 0.05 to about 25 ⁇ S/cm, more specifically about 0.05 to about 10 ⁇ S/cm. In one advantageous embodiment, the heat transfer fluid has an electrical conductivity of about 0.05 to about 5 ⁇ S/cm.
  • the heat transfer fluid can be prepared by mixing the different components together and homogenizing the resulting mixture.
  • the alcohol and water are advantageously mixed together first.
  • the other components and additives are then added to the alcohol-water mixture by mixing and adequate stirring.
  • the alcohol is mixed with the other components first, excluding the water.
  • the resulting mixture is then homogenized.
  • Water can then be added prior to packaging and/or prior to use of the heat transfer fluid.
  • the heat transfer fluid can be used in a variety of assemblies. It is advantageous to use the heat transfer fluid in assemblies comprising heat transfer systems which comprise aluminum and/or magnesium, and wherein the heat transfer fluid, once introduced into the heat transfer system, is in contact with the aluminum and/or magnesium. It is also advantageous to use the heat transfer fluid in assemblies where the heat transfer fluid is exposed to an electrical current (such as in fuel cells, and the like).
  • the assemblies comprise internal combustion engines or alternative power sources, among others.
  • Internal combustion engines include those that are powered by gasoline, and also those that are powered by natural gas, diesel, methanol, hydrogen, the condensation of steam, and/or the like.
  • Non- limiting examples of alternative power sources include batteries, fuel cells, solar cells, solar panels, photovoltaic cells.
  • Alternative power sources can include devices powered by internal combustion engines operating with a clean heat transfer system, that is, a heat transfer system that does not contribute to the concentration of ionic species in the heat transfer fluid. Such alternative power sources can be used alone or in combination, such as those employed in hybrid vehicles.
  • Assemblies comprising such alternative power sources include any assembly that can traditionally be powered by an internal combustion engine, such as automotive vehicles, boats, generators, lights, aircrafts, airplanes, trains, locomotives, military transport vehicles, stationary engines, and the like.
  • the assemblies also include additional systems or devices required for the proper utilization of power sources, such as electric motors, DC/DC converters, DC/AC inverters, electric generators, and other power electronic devices, and the like.
  • the disclosed assemblies include a power source comprising a heat transfer system in thermal communication with the alternative power source and with the heat transfer fluid.
  • the heat transfer system comprises a circulation loop defining a flow path for the heat transfer fluid.
  • the heat transfer system can be integrated with the power source, that is, the power source can be a part of the heat transfer system.
  • the heat transfer system comprises a circulation loop defining a flow path for the heat transfer fluid, the circulation loop flowing through the power source.
  • a heat transfer system comprises a circulation loop defining a flow path for a heat transfer fluid, and a heat transfer fluid comprising a liquid coolant, a siloxane corrosion inhibitor, and a non-conductive polydiorganosiloxane antifoam agent, wherein the conductivity of the heat transfer fluid is less than about 100 ⁇ S/cm, and wherein the heat transfer system comprises aluminum, magnesium, or a combination thereof, in intimate contact with the heat transfer fluid.
  • the power source is an internal combustion engine
  • the heat transfer system comprises magnesium.
  • FIG. 1 refers to an exemplary embodiment wherein the heat transfer system comprises magnesium, it is not limited thereto and can also comprise aluminum, or the like. A combination of the metals can also be used.
  • an exemplary heat transfer system 10 comprises a heat transfer fluid reservoir 12, a pump 14, an engine 16, a heater core 18, a thermostat 20, a radiator cap 22, an overflow tank 26 and a radiator 24.
  • the heat transfer system can further comprise an ion exchange resin 28, conduits (e.g., pipe 30), valves (not shown) and other pumps.
  • Each component of the heat transfer system 10 can comprise magnesium.
  • at least one of the components of the heat transfer system 10 comprises magnesium and/or magnesium alloys.
  • each of the pump 14, the engine 16, the heater core 18, the thermostat 20, the radiator cap 22, the overflow tank 26, and the radiator 24 comprises magnesium.
  • one or more components comprise magnesium while one or more other components comprise aluminum.
  • the reservoir 12 is provided to maintain the heat transfer fluid in an environment free from undesirable contaminants when the fluid is not circulating.
  • reservoir 12 comprises plastic.
  • the pump 14 is provided to drive the fluid through the heat transfer system 10. Specifically, pump 14 routes fluid from the reservoir, through an engine block of the engine 16, that is, through a first set of interior passages of the engine that are disposed proximate the engine cylinder, through heater core 18, through a second set of interior passages of the engine block, and to the thermostat 20. Depending on the position of the thermostat 20, the fluid is then routed through either the radiator cap 22, the radiator 24, then to the pump 14, or directly to the pump 14.
  • the pump 14 can be a centrifugal pump driven by a belt connected to a crankshaft of the engine 16.
  • the pump 14 pumps heat transfer fluid through the heat transfer system 10 when the engine 16 is operating.
  • the pump 14 can comprise a rotating component comprising an impeller and a shaft.
  • the pump 14 can further comprise a stationary component comprising a casing, a casing cover, and bearings.
  • a stationary component comprising a casing, a casing cover, and bearings.
  • both the rotating component of the pump and the casing component of the pump comprise magnesium.
  • only the rotating component, the casing component, or subcomponents of the rotating component and casing component comprise magnesium.
  • the engine 16 comprises the engine block, cylinders, cylinder connecting rods, and a crankshaft.
  • the engine block comprises internal passageways disposed therethrough.
  • the internal passageway can be cast or machined in the engine block.
  • the heat transfer fluid can be routed through the internal passageways of the engine to transfer heat from the engine. These passageways direct the heat transfer so that the fluid can transfer heat away from the engine to optimize engine performance.
  • the metal engine components comprise magnesium.
  • the engine block, the cylinders, the cylinder connecting rods, and the crankshaft comprise magnesium.
  • certain engine components can comprise magnesium, while other engine components do not comprise magnesium.
  • the engine block can comprise magnesium, while the cylinder, cylinder connecting rods, and the crankshaft can comprise steel.
  • the heater core 18 is provided to cool the heat transfer fluid while heating a vehicle interior.
  • the heater core 18 can comprise a series of thin flattened tubes having a high interior surface area and exterior surface area such that heat can be effectively transferred away from the heat transfer fluid.
  • the heating core 18 comprises magnesium tubes brazed together.
  • the heating core can comprise tubes joined together by other joining methods or the heating core can be cast as a single unit. Air can be forced past the heater core to increase the cooling rate of the heat transfer fluid.
  • the thermostat 20 is provided to measure a temperature indicative of a selected heat transfer fluid temperature and selectively routes the heat transfer fluid to the radiator or to the pump. Thermostat 20 routes the heat transfer fluid to the radiator when the temperature of the heat transfer fluid is greater than or equal to the selected temperature and to the pump when the temperature of the heat transfer fluid is less than the selected temperature.
  • the thermostat has an inlet portion, a radiator outlet portion, a radiator bypass outlet portion, and a valve portion.
  • a single housing member can define the inlet portion, the radiator outlet portion, and the radiator bypass outlet portion.
  • the valve portion can be disposed within the single housing member and provide selective communication between the inlet portion and both the radiator outlet portion and the radiator bypass outlet portion.
  • the thermostat When the valve is in a closed position, the thermostat routes the heat transfer fluid directly to the pump.
  • the thermostat When the valve is in the open position, the thermostat routes the heat transfer fluid through the radiator.
  • the thermostat valve portion and the thermostat housing member comprise magnesium. In another exemplary embodiment, only the housing or only the valve portion comprise magnesium
  • the radiator cap 22 is provided to seal the heat transfer system and to maintain the heat transfer fluid at a selected pressure to prevent the heat transfer fluid from boiling.
  • the radiator cap 22 comprises magnesium.
  • the radiator 24 is provided to cool the heat transfer fluid.
  • the radiator 24 can comprise a series of thin flattened tubes having a high interior surface area and exterior surface area such that heat can be effectively transferred from the heat transfer fluid.
  • the radiator 24 comprises magnesium tubes brazed together.
  • the radiator can comprise tubes joined together by other joining methods or case as a single unit. Air can be forced past the radiator to increasing the cooling rate of the heat transfer fluid.
  • the optional ion exchange resin (not shown) exchanges ions with the heat transfer fluid. Specifically, the ion exchange resin removes corrosive ions from the heat transfer fluid and replaces the corrosive ions with ions that reduce the caustic properties of the heat transfer fluid.
  • the ion exchange resin is in fluid communication with the heat transfer fluid, and with the flow path and/or circulation loop defined by the heat transfer system.
  • the heat transfer system 10 comprises an ion exchange resin.
  • the ion exchange resin is disposed between the engine and the thermostat.
  • the ion exchange resin is disposed in other locations of the heat transfer system 10.
  • the ion exchange resin is disposed between other heat transfer system components.
  • the ion exchange resin can be disposed within the heat transfer system components, such as in the heat transfer fluid reservoir.
  • Non-limiting examples of ion exchange resins include anion exchange resins, cation exchange resins, mixed bed ion exchange resins, and combinations thereof.
  • the ion exchange resin comprises a polymer matrix comprising polymers comprising functional groups paired with an exchangeable ion.
  • the exchangeable ion is generally one or more OfNa + , H + , OFF, or Cl " ions, depending on the type of ion exchange resin.
  • Non-limiting examples of polymers comprised in the polymer matrix include polystyrene, polystyrene and styrene copolymers, polyacrylates, aromatic substituted vinyl copolymers, polymethacrylates, phenol-formaldehyde, polyalkylamine, and the like, and combinations thereof.
  • the polymer matrix comprises polystyrene and styrene copolymers, polyacrylates, or polymethacrylates, while in one exemplary embodiment, the polymer matrix comprises styrenedivinylbenzene copolymers.
  • Non-limiting examples of functional groups in cation ion exchange resins include sulfonic acid groups (-SO3H), phosphonic acid groups (-PO3H), phosphinic acid groups (- PO 2 H), carboxylic acid groups (-COOH or -C(CH 3 )-COOH), and the like, and combinations thereof.
  • the functional groups in the cation exchange resin are -SO 3 H, -PO 3 H, or -COOH, while in one exemplary embodiment, the functional groups in the cation exchange resin are -SO3H.
  • Non-limiting examples of functional groups in anion exchange resins include quaternary ammonium groups such as benzyltrimethylammonium groups, termed type 1 resins, benzyldimethylethanolammonium groups, termed type 2 resins, trialkylbenzyl ammonium groups, also termed type 1 resins, tertiary amine functional groups, and the like.
  • the functional groups in the anion exchange resin are benzyltrimethylammonium, or dimethyl-2-hydroxyethylbenzyl ammonium, while in one exemplary embodiment the functional groups in the anion exchange resin are benzyltrimethylammonium.
  • the particular ion exchange resin selected is dependent upon the composition of the heat transfer fluid, and can exchange ions with any ionic species produced by the heat transfer fluid.
  • the ion exchange resin should be a mixed bed resin, an anion exchange resin, or a combination thereof.
  • Commercially available anion exchange resins typically comprise OH " or Cl " exchangeable ions. In one embodiment, the exchangeable ion is OH " .
  • the siloxane corrosion inhibitor, the non-conductive polydimethylsiloxane antifoam agent, the azole, or any additive in the heat transfer fluid are likely to become positively charged, then mixed bed resins, cation exchange resins or a combination thereof should be used.
  • Commercially available cation exchange resins typically comprise H + or Na + exchangeable ions. In one embodiment, the exchangeable ion is H + .
  • ion exchange resins suitable for use herein are available from Rohm & Haas of Philadelphia, PA as AMBERLITE, AMBERJET, DUOLITE, and IMAC resins, from Bayer of Leverkusen, Germany as LEWATIT resin, from Dow Chemical of Midland, MI as DOWEX resin, from Mitsubishi Chemical of Tokyo, Japan as DIAION and RELITE resins, from Purolite of BaIa Cynwyd, PA as PUROLITE resin, from Sybron of Birmingham, NJ as IONAC resin, from Resintech of West Berlin, NJ, and the like.
  • the suitable commercially available ion exchange resin is DOWEX MR-3 LC NG Mix mixed bed resin, DOWEX MR-450 UPW mixed bed resin, IONEC NM-60 mixed bed resin, or AMBERLITE MB- 150 mixed bed resin, while in one exemplary embodiment, the suitable commercially available ion exchange resin is DOWEX MR-3 LC NG Mix.
  • the ion exchange resin is pre-treated with a corrosion inhibiting composition prior to use in the heat transfer system.
  • the ion exchange resin is pre-treated by contacting the ion exchange resins with an aqueous corrosion inhibiting solution comprising the corrosion inhibiting composition for a selected time period.
  • the ion exchange resin is contacted with the aqueous corrosion inhibiting composition solution for a period of time sufficient to allow the corrosion inhibiting composition to exchange ions with at least about 15% of the total exchangeable ions, based on the total number of exchangeable ions in the ion exchange resin. That is, the corrosion inhibiting composition loading of the corrosion inhibiting composition treated ion exchange resin should be at least about 15% of the exchange capacity of the ion exchange resin.
  • the period of contact is sufficient to allow the corrosion inhibiting compositions to exchange ions with at least about 50% of the total exchangeable ions, based on the total number of exchangeable ions in the ion exchange resin. In one exemplary embodiment, the period of contact is sufficient to allow the corrosion inhibiting composition to exchange ions with at least about 75% of the total exchangeable ions, based on the total number of exchangeable ions in the ion exchange resin.
  • the period of contact is sufficient to allow the corrosion inhibiting composition loading of the corrosion inhibiting composition treated ion exchange resin to be an amount of about 15 to about 99% of the total exchange capacity of the ion exchange resin or from about 15 to about 99% of the total exchangeable ions, based on the total number of exchangeable ions in the ion exchange resin.
  • the resultant corrosion inhibiting composition treated ion exchange resins will be cleansed with de-ionized water and/or the heat transfer fluid to minimize the chance for accidental introduction of impurities.
  • ion exchange resins in Na + or Cl " forms are used only if the treatment with the aqueous corrosion inhibiting solution results in the removal of substantially all of the Na + or Cl " ions from the ion exchange resin. In one embodiment, ion exchange resins in Na + or Cl " forms are used if the treatment with the aqueous corrosion inhibiting solution results in the corrosion inhibiting composition loading of the corrosion inhibiting composition treated ion exchange resin being at least about 80% of the total exchangeable ions.
  • the corrosion inhibiting compositions for treating the ion exchange resin comprises a siloxane corrosion inhibitor, an azole, or a combination thereof. Suitable siloxane corrosion inhibitors and azoles are those described above.
  • the corrosion inhibiting compositions are weakly ionic and therefore, when in contact with the heat transfer fluid, maintain the low conductivity of the heat transfer fluid.
  • the amount of corrosion inhibiting composition released from the resin depends on the level of corrosive ions in the heat transfer fluid.
  • the corrosion inhibiting composition is advantageous since an increase in the amount of corrosive ions in the heat transfer fluid produces an increase in the amount of corrosion inhibiting composition from the resin being released into the heat transfer fluid due to the ion exchange mechanism.
  • the increase in the amount of corrosion inhibiting composition concentration in the heat transfer fluid will lead to a reduction in the corrosion rate.
  • Another advantage of the heat transfer system is that the presence of the ion exchange rein, and advantageously, the mixed bed ion exchange resin, will also maintain low conductivity in the heat transfer fluids in the system.
  • acidic aqueous corrosion inhibiting solutions suitable for treating the ion exchange resin have a pK a value of equal to or greater than about 5 at 25° C, specifically from about 5 to about 14.
  • basic aqueous corrosion inhibiting solutions suitable for treating the ion exchange resin have a pKb value of equal to or greater than about 5 at 25° C, specifically from about 5 to about 14.
  • the ion exchange resin can be treated with other additives such as colorants, wetting agents, antifoam agents, biocides, and nonionic dispersants, with the proviso that the other additives do not substantially increase the overall electrical conductivity of the heat transfer fluid when the additives are added to the heat transfer fluid.
  • additives such as colorants, wetting agents, antifoam agents, biocides, and nonionic dispersants
  • the ion exchange resin will be treated with a non-conductive polydimethylsiloxane emulsion based antifoam.
  • Suitable polydimethylsiloxane emulsion based antifoams include those described above.
  • an assembly comprises a power source that can be an internal combustion engine, or advantageously, an alternative power source, specifically a solar cell or fuel cell.
  • the heat transfer system comprises magnesium.
  • the assembly can also comprise a regenerative braking system. It will be understood that while FIG. 2 refers to an exemplary embodiment wherein the heat transfer system comprises magnesium or aluminum, any other susceptible metal can be used therein.
  • an exemplary heat transfer system 116 comprises an internal combustion engine 105, or fuel cells 105 or solar cells 105 as the primary power source 107. It also comprises a rechargeable secondary battery 112 or an optional ultra-capacitor 113 that can be charged via the assembly's regenerative braking system. The battery 112 and/or the ultra-capacitor 113 can act as secondary power sources.
  • the assembly can further comprise power electronic devices, such as DC/DC converters 110, DC/ AC inverters 110, generators 108, power splitting devices 109, and/or voltage boost converters 111, and the like.
  • the assembly can contain fuel cell or solar cell "balance of plant" subsystems 106.
  • the assembly also comprises HAVC systems 114, such as, air- conditioning system for the climate control of assembly interior space.
  • the heat transfer system 116 further comprises a pump 101, heat transfer fluid flow path 104, heat transfer fluid tank 102, and a radiator or heat exchanger 103, and a fan 115.
  • the fan can be substituted by an external cooling source, such as a different (or isolated) cooling system with its own cooling media.
  • An ion exchange resin (not shown) can also be present, and is as described above.
  • the alternative power source is a fuel cell.
  • the fuel cell is in thermal communication with the heat transfer systems and fluids.
  • the electrical conductivity of the heat transfer fluids is less than about 10 ⁇ S/cm.
  • the heat transfer fluid comprises an electrical conductivity of about 0.02 to about 10 ⁇ S/cm.
  • the heat transfer fluid comprises an electrical conductivity of about 0.05 to about 5 ⁇ S/cm.
  • the heat transfer fluid can be used in a number of different types of fuel cells comprising an electrode assembly comprising an anode, a cathode, and an electrolyte, and a heat transfer fluid in thermal communication with the electrode assembly or fuel cell.
  • the heat transfer fluid can be contained or flow in channel or flow path defined by a circulation loop or heat transfer fluid flow channel in thermal communication with the fuel cell.
  • Non- limiting examples of fuel cells include PEM (Proton Exchange Membrane or Polymer Electrolyte Membrane) fuel cells, AFC (alkaline fuel cell), PAFC (phosphoric acid fuel cell), MCFC (molten carbonate fuel cell), SOFC (solid oxide fuel cell), and the like.
  • PEM Proton Exchange Membrane or Polymer Electrolyte Membrane
  • AFC alkaline fuel cell
  • PAFC phosphoric acid fuel cell
  • MCFC molten carbonate fuel cell
  • SOFC solid oxide fuel cell
  • the heat transfer fluid is used in PEM and AFC fuel cells.
  • Table 1 illustrates the composition of heat transfer fluids, represented by Fn, with n being the number of the fluid.
  • Table 2 illustrates the corrosion results obtained in a galvanic couple where a MRI202S magnesium alloy anode is galvanically coupled to a copper cathode.
  • a 0.5 square centimeter magnesium alloy coupon is placed in a heat transfer fluid along with a 1.1 square centimeter copper alloy coupon.
  • the coupons are placed 1 centimeter apart and the temperature is maintained at 88° C.
  • Conductivity, average corrosion rate, and corrosion loss level results of the magnesium alloys in solution are listed below. In each example magnesium corrosion loss was measured over a total time of 12,000 seconds. En refers to Example, wherein n is the number of the example.
  • the test solutions used are described in Table 1.
  • the galvanic couple current density is measured as a function of time. In general, the current density is varied over time.
  • the total charge in Table 2 represents the total amount of the galvanic corrosion occurring during a test.
  • Average corrosion rate and corrosion loss data are calculated by using the total charge and total time of the test according to the Faraday law and expected corrosion anodic reaction, i.e., Mg — > Mg 2+ + 2e " .
  • Final galvanic couple current density represents the instant galvanic corrosion rate of the magnesium alloy at the end of the test. In general, if the average corrosion rate and the corrosion loss value is lower for a given inhibitive coolant formulation, it indicates that the coolant formulation is providing a better corrosion protection than a coolant formulation that yields a higher corrosion rate.
  • Resin 1 comprises 3 grams of DOWEX MR-450 UPW.
  • Resin 2 comprises 3.5 grams of Amberjet UP6040 ion exchange resin, treated with an aqueous benzotriazole solution.
  • Resin 3 comprises 7.0 grams of DOWEX MR-450 UPW and 1.75 grams of untreated Amberjet UP6040.
  • Resin 4 comprises 7.0 grams of DOWEX MR-450 UPW treated with an aqueous benzotriazole solution.
  • Resin 5 comprises 14.35 grams of Dowex MR-450 UPW treated with an aqueous benzotriazole solution and 3.5 grams of untreated DOWEX MR-450 UPW.
  • the dry resin is the resin refers to the resin as received from the supplier.
  • the wet resin refers to the resin treated with an aqueous benzotriazole solution.
  • the resin after treatment was recovered from the treatment container, i.e., a pyrex beaker, using a stainless steel spatula.
  • the resin was then transferred to a clean and inert ion exchange resin filter bag made of Nylon.
  • the excess amount of water was drained by the force of gravity. After the excess amount of water was removed from the treated resin, the resin was stored in a clean glass bottle for later use.
  • the benzotriazole pretreatment of the resin was typically conducted by adding 1Og of Dowex MR-450 UPW mixed bed ion exchange resin into 1 liter of deionized water.
  • benzotriazole treated resin Before adding the ion exchange resin, 1200 mg/L benzotriazole was dissolved in the 1 liter of the deionized water. Under constant magnetic stirring via the use of a Teflon coated magnet stirring bar and a magnetic stirrer, the resin and the benzotriazole aqueous solution were allowed to react for 22 hours at room temperature. During this treatment process, benzotriazole is exchanged with H + and OH " groups in the mixed bed ion exchange resin so that the resin is saturated with benzotriazole at all the exchangeable sites. The mixed bed ion exchange resin obtained after the treatment is termed the benzotriazole treated resin.
  • Table 3 illustrates the test results obtained in galvanic couple corrosion experiments where a MRI202S magnesium alloy anode is galvanically coupled to a mild steel ClOl 8 cathode.
  • a 0.5 square centimeter magnesium alloy coupon is placed in a heat transfer fluid along with a 1.1 square centimeter steel coupon.
  • the coupons are placed 1 centimeter apart and the temperature is maintained at 88° C.
  • Conductivity, average corrosion rate, and corrosion loss level results of the magnesium alloys in solution are listed below. In each example magnesium corrosion loss was measured over a total time of 12,000 seconds.
  • Resin 6 comprises 10 grams of MR-450 UPW treated with an aqueous benzotriazole solution and 3 grams of MR-450UPW.
  • Resin 7 comprises 10 grams of MR-450 UPW treated with an aqueous benzotriazole solution and 3.7 grams of MR-450UPW.
  • the heat transfer fluids lacking the siloxane corrosion inhibitor and non-conductive polydimethylsiloxane antifoam agent has an average corrosion loss rate of greater than 0.3 and up to as high as about 215 ⁇ m/day for
  • the examples with a siloxane corrosion inhibitor, an azole and a non-conductive polydimethylsiloxane antifoam agent have a magnesium average corrosion loss rates of less than 2.1 ⁇ m/day. It can also be seen that the benzotriazole-treated ion exchange resins can be used to keep the conductivity similar to when untreated ion exchange resins are used, and the same time allow the presence of benzotriazole residual concentration in the heat transfer fluid to provide the desirable corrosion protection for copper based alloys and other metals in the heat transfer system.
  • Tables 5 and 6 illustrate the test results obtained in galvanic couple corrosion tests where galvanic couples C1-C5 of Table 4 were used. These galvanic couples are exemplary magnesium-based compositions for use in automotive magnesium-based heat transfer systems, among others.
  • the mass loss was determined according to a modified ASTM-D1384 procedure.
  • the ASTM-D1384 test was modified by using different arrangement of metal coupons as described in Table 4.
  • the metals galvanically coupled through heat transfer fluids that comprise a siloxane corrosion inhibitor, and a non-conductive polydimethylsiloxane antifoam agent exhibit substantially less weight loss due to corrosion than metals galvanically coupled through heat transfer fluids which lack the siloxane corrosion inhibitor, and a non-conductive polydimethylsiloxane antifoam agent (Table 5).
  • Example 27 comprises a UP6040 resin and Example 28 comprises a DOWEX MR-3 LC NG Mix resin.
  • Example 29 illustrates the results for Example 29. 9.7 g of the resin was first immersed in 1000 g of a 50 wt% ethylene glycol aqueous solution comprising 1300 ppm tolyltriazole, and stirred for 22 hours. 1 g of the resulting pretreated resin was then immersed in 100 g of a 50:50 ethyleneglycol:deionized water solution comprising 30 ppm sodium formate and 30 ppm sodium acetate and stirred.
  • Example 29 comprises a DOWEX MR-3 LC NG Mix Resin.
  • Example 30 was a blank resin conductivity test.
  • 1O g of MTO-DOWEX MR-3 LC NG Mix resin were pretreated by immersing in 25Og of a 50wt% ethylene glycol aqueous solution comprising 1200 ppm benzotriazole.
  • 10 g of MTO-DOWEX MR-3 LC NG Mix resin were pretreated by immersing in 50Og of a 50wt% ethylene glycol aqueous solution comprising 1200 ppm benzotriazole.
  • 1 g of the treated resin was immersed in lOOg of a 50wt% ethylene glycol solution comprising 30 ppm NaCl and stirred.
  • Example 10 illustrates the results for Examples 33-35.
  • 10 g of MTO-DOWEX MR-3 LC NG Mix resin were pretreated by immersing in 75Og of a 50wt% ethylene glycol aqueous solution comprising 1200 ppm benzotriazole.
  • 10 g of MTO-DOWEX MR-3 LC NG Mix resin were pretreated by immersing in lOOOg of a 50wt% ethylene glycol aqueous solution comprising 1200 ppm benzotriazole.
  • Example 35 10 g of MTO-DOWEX MR-3 LC NG Mix resin were pretreated by immersing in lOOOg of a 50wt% ethylene glycol aqueous solution comprising 1300 ppm tolyltriazole. 1 g of the treated resin was immersed in lOOg of a 50wt% ethylene glycol solution comprising 30 ppm NaCl and stirred. Table 10
  • benzotriazole and tolyltriazole treated resins are effective at removing undesirable ionic impurities such as Na+, Cl-, formate, and acetate and thus reducing the conductivity of the thermal exchange fluid while keeping the conductivity at a low level.
  • the benzotriazole or tolyltriazole treated ion exchange resin can also leave a desirable residual amount of the triazole in the heat transfer fluid as can be seen in Examples 33-35, and thus maintaining effective corrosion protection for metals in the heat transfer system.
  • substituted means that any one or more hydrogen atoms on the designated atom or group is replaced with a selection from the indicated group, provided that the designated atom's normal valence is not exceeded.
  • alkyl includes both branched and straight chain saturated aliphatic hydrocarbon groups, having the specified number of carbon atoms.
  • C 1 -C 7 alkyl as used herein indicates an alkyl group having from 1 to about 7 carbon atoms.
  • Co-C p alkyl is used herein in conjunction with another group, for example, heterocycloalkyl (Co-C 2 alkyl)
  • the indicated group in this case heterocycloalkyl, is either directly bound by a single covalent bond (Co), or attached by an alkyl chain having the specified number of carbon atoms, in this case from 1 to p carbon atoms.
  • alkyl examples include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, 3-methylbutyl, t-butyl, n-pentyl, and sec-pentyl.
  • non-conductive as used herein relates to a species that produces a conductivity increase of less than about 10 ⁇ S/cm when introduced into a standard solution of deionized water, at a maximum concentration of no more than 0.2 % by weight, based on the total weight of the standard solution.
  • Substantially free of as used herein refers to an amount that is not in excess of an amount that will lead to the conductivity of the heat transfer fluid to increase by more than 10 ⁇ S/cm.
  • Alternative power sources refers to power source technologies that provide improvements in energy efficiency, environmental concerns, waste production, and management issues, natural resource management, and the like.
  • Metal refers to the element metal, wherein “metal alloy” or “metallic alloy” refers to the metal in combination with one or more other metals.
  • metal alloy refers to the element magnesium
  • a magnesium alloy refers to a combination of magnesium with one or more other metals.
  • a magnesium alloy comprises magnesium, and a system comprising magnesium can comprise either elemental magnesium alone, a magnesium alloy, or a combination of elemental magnesium and a magnesium alloy.
  • High conductivity refers to a conductivity of greater than 100 ⁇ S/cm.

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Abstract

L'invention concerne un système de transfert thermique comprenant une boucle de circulation définissant un trajet d'écoulement pour un fluide de transfert thermique, et un fluide de transfert thermique comprenant un frigorigène liquide, un inhibiteur de corrosion de siloxane de formule R3-Si-[O-Si(R)2]x-OSiR3, R étant indépendamment un groupe alkyle ou un copolymère d'oxyde de polyalkylène ayant de 1 à 200 atomes de carbone, x étant un nombre entier de 0 à 100, et en outre dans lequel au moins un groupe alkyle et au moins un copolymère d'oxyde de polyalkylène sont présents, ainsi qu'un agent antimousse de polydiorganosiloxane non conducteur, la conductivité du fluide transfert thermique étant inférieure à environ 100 µS/cm, et le système de transfert thermique comprenant de l'aluminium, du magnésium, ou une combinaison de ceux-ci, en contact intime avec le fluide de transfert thermique.
EP09795240.2A 2008-07-11 2009-07-10 Système de transfert thermique, fluide, et procédé Withdrawn EP2300553A4 (fr)

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