BR112019000586B1 - HEAT TRANSFER FLUIDS AND METHODS FOR PREVENTING CORROSION IN HEAT TRANSFER SYSTEMS - Google Patents

Abstract

The present invention relates to heat transfer fluid concentrates that include: a freezing point depressant, water or a combination thereof; an organophosphate; a carboxylic acid or a salt thereof; and a component selected from the group consisting of an alkaline earth metal ion, an alkali metal ion, a transition metal ion, an inorganic phosphate, molybdate ion, nitrate ion, nitrite ion, an azole compound, an inhibitor of corrosion of copper and copper alloy, a silicate, a silicate stabilizer, a water-soluble polymer and combinations thereof. Ready-to-use heat transfer fluids and methods for preventing corrosion in heat transfer systems are described.

Description

TECHNICAL FIELD

[0001] The present invention relates generally to heat transfer fluids and, in some embodiments, to heat transfer fluids for inhibiting corrosion in heat transfer systems.

BACKGROUND

[0002] Modern vehicle engines generally require a heat transfer fluid (liquid coolant) to provide year-round, long-lasting protection of their cooling systems. The main requirements of heat transfer fluids are that they provide efficient heat transfer to control and maintain engine temperature for efficient fuel economy and lubrication and to prevent engine failures due to freezing, boiling or overheating. An additional key requirement of a heat transfer fluid is that it provides corrosion protection of all metals in the cooling system over a wide range of temperatures and operating conditions. Aluminum corrosion protection for engine block, cylinder head, water pump, heat exchangers and other components made of aluminum or aluminum alloys is particularly important. In addition to metal protection, corrosion protection helps the heat transfer fluid perform its primary function of transferring excess heat from the engine to the radiator for dissipation.

[0003] Common corrosion-related problems that can arise in automotive cooling systems include: (1) cavitation corrosion and rust of cylinder heads and cylinder blocks; (2) seal leakage, bellows seal failure and cavitation corrosion in water pumps; (3) formation of solder bloom, residue and deposits, and localized corrosion on radiators and heater cores; (4) stuck thermostat; and/or (5) crevice corrosion on hose necks. Furthermore, erosion-corrosion, galvanic corrosion, deposit corrosion and/or stray current corrosion can occur in susceptible locations in a cooling system depending on the conditions.

[0004] Different types of metals can be used to manufacture the various parts of a cooling system. By way of example, cast iron and cast aluminum alloys can be used for cylinder blocks, cylinder heads, inlet hoses, coolant pumps, and power electronic device housings; forged aluminum and copper alloys can be used for radiators and heater cores; solders can be used to join bronze and copper radiator components or heater cores; steel can be used for cylinder head gaskets and for small components such as coolant plugs and coolant pump housing cases and coolant pump impellers; and copper alloys can be used in thermostats.

[0005] Rapid depletion of key corrosion inhibitors (e.g., nitrite) in engine coolants, along with substantial increase in pH of coolant solutions, has been observed in the field and also confirmed in laboratory tests. Such changes to a refrigerant can negatively impact its corrosion protection performance and affect its stability. The results demonstrate that such changes in coolant are most pronounced after contact with the aluminum surfaces of heat exchangers manufactured by a controlled atmosphere brazing (CAB) technique under engine cooling system operating conditions. The potassium fluoroluminate flux residue left on aluminum surfaces from the CAB process can play a key role in changing the chemical properties and protective performance of engine coolants. The development of more compact, lighter engines to improve fuel economy, and the increasing use of aluminum heat exchangers produced by the CAB technique in engine cooling systems to replace those previously manufactured by other techniques (e.g. assembly mechanics or vacuum brazing) may contribute to the changes observed in engine coolants during field use.

[0006] Protection against corrosion of components made of aluminum or aluminum alloys (e.g. engine block, cylinder head, water pump, heat exchangers and similar), protection against corrosion of components of the heat transfer system produced by the CAB process (e.g., heat exchangers) and high-temperature corrosion protection (e.g., in cooling systems for vehicles equipped with exhaust gas recirculation or EGR) are of interest.

SUMMARY

[0007] The scope of the present invention is defined only by the appended claims and is not affected to any degree by the statements in this summary.

[0008] By way of introduction, a first heat transfer fluid concentrate in accordance with the present teachings includes (a) a freezing point depressant, water or a combination thereof; (b) an organophosphate; (c) a carboxylic acid or a salt thereof; and (d) a component selected from the group consisting of an alkaline earth metal ion, an alkali metal ion, a transition metal ion, an inorganic phosphate, molybdate ion, nitrate ion, an azole compound, a corrosion inhibitor of copper and copper alloy, a silicate, a silicate stabilizer, a water-soluble polymer and combinations thereof.

[0009] A second heat transfer fluid concentrate in accordance with the present teachings includes (a) a freezing point depressant, water, or a combination thereof, where the freezing point depressant is present in a varying amount from about 1% by weight to about 99% by weight, based on a total weight of the heat transfer fluid concentrate; (b) an organophosphate, wherein the organophosphate is present in an amount ranging from about 0.002% by weight to about 5% by weight based on the total weight of the heat transfer fluid concentrate; (c) a carboxylic acid or a salt thereof, wherein the carboxylic acid or salt thereof is present in an amount ranging from about 1% by weight to about 10% by weight based on the total weight of the heat transfer fluid concentrate, wherein the carboxylic acid includes one or a plurality of C6 to C20 carboxylic acids, and where the one or plurality of C6 to C20 carboxylic acids is individually selected from the group consisting of an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, an aromatic monocarboxylic acid, an aromatic dicarboxylic acid and combinations thereof; (d) calcium ion at a concentration of up to about 200 mg/L based on a total weight of the heat transfer fluid concentrate; (e) magnesium ion at a concentration of up to about 150 mg/L based on a total weight of the heat transfer fluid concentrate; (f) an azole compound present in an amount ranging from about 0.01% by weight to about 3% by weight based on the total weight of the heat transfer fluid concentrate; and (g) optionally, an added component selected from the group consisting of an inorganic phosphate, lithium ion, zinc ion, nitrate ion, nitrite ion, molybdate ion, a phosphonate, a phosphinate, an acrylate-based polymer , a dye, a biocide, an antifoam, a surfactant, a dispersant, an anti-particle deposition agent, a wetting agent and combinations thereof.

[0010] A ready-to-use heat transfer fluid in accordance with the present teachings includes water and a heat transfer fluid concentrate of a type described above. The heat transfer fluid concentrate is present in an amount ranging from about 30% by volume to about 60% by volume based on a total volume of the heat transfer fluid.

[0011] A method in accordance with the present teachings for preventing corrosion in a heat transfer system includes contacting at least a portion of the heat transfer system with a heat transfer fluid of a type described above.

BRIEF DESCRIPTION OF THE DESIGN

[0012] Figure 1 shows the anodic polarization curve measurements obtained on an AA319 cast aluminum alloy electrode immersed in 25% vol refrigerant concentrate. + 100 ppm chloride ions for 6 hours under heat transfer heat rejection conditions.

DETAILED DESCRIPTION

[0013] To ensure long service life and satisfy design functions, metal components used in automotive cooling systems must be protected from corrosion by an engine coolant. Furthermore, an engine coolant must be compatible with non-metals (such as hoses, gaskets and plastics) used in cooling systems. Corrosion or excessive degradation of material used in cooling systems can lead to a substantial reduction in the strength of a material or component, loss of refrigerant to the system, and subsequent malfunction of one or more of the cooling system components. All of these events can result in engine failure. Furthermore, even relatively mild corrosion can result in the formation of corrosion products that can form scale or deposits on heat transfer surfaces. These scales or deposits can greatly reduce the rate of heat transfer. The thermal conductivity for a non-porous scale is about 1.04 to 3.46 W/mK at 25° C and that of deposit or porous scale can be about 0.35 W/mK at 25° C. These values are much lower than the thermal conductivities of several metals used in cooling systems (e.g., 401 W/mK at 25° C for copper; 250 W/mK at 25° C for aluminum, 156 W/mK at 25° C for magnesium, 109 W/mK @ 25° C for admiralty brass, 55 W/mK @ 25° C for cast iron, or 16 W/mK @ 25° C for stainless steel). In summary, the thermal conductivity of scale and deposits is in the range of a refractory brick that is used as a heat insulating material at 500°C (1.4 W/mK). Deposition of excessive scale or corrosion product can also lead to restricted coolant flow in the radiator and heater core tubes, even plugging the heater core and/or radiator. Substantial heat transfer rate reduction and coolant flow restriction can lead to engine overheating.

[0014] In addition to providing reliable corrosion protection for various metallic components in cooling systems, an engine coolant must also have the following properties to satisfy all requirements for use as a year-round functional fluid for a vehicle : high thermal conductivity; high heat capacity or high specific heat; good fluidity within the temperature range of use; high boiling point; low freezing point; low viscosity; low toxicity and safety of use; cost effectiveness and adequacy of supply; chemically stable at temperature and conditions of use; tendency to little foaming; and good material compatibility (i.e., does not corrode, erode or degrade system materials - including both metallic and non-metallic materials). The heat transfer fluid concentrates described below can be used to provide one or more of the properties described above.

[0015] In accordance with the present teachings, heat transfer fluid concentrates and ready-to-use heat transfer fluids derived from heat transfer fluid concentrates (e.g., through dilution with water) exhibit a synergistic effect between the components of the formulation with respect to corrosion inhibition. As described further below, synergistic heat transfer fluid concentrates and ready-to-use heat transfer fluids derived therefrom contain one or more organophosphates (also known as phosphate esters).

[0016] Throughout this application and the appended claims, the following definitions must be understood.

[0017] The term "heteroatom" refers to any atom other than carbon and hydrogen. Representative examples of heteroatoms in accordance with the present teachings include, but are not limited to, nitrogen, oxygen, sulfur and the like.

[0018] The term "alkyl" refers to a substituted or unsubstituted, straight, branched or cyclic hydrocarbon chain containing, in some embodiments, from 1 to 24 carbon atoms. Representative examples of unsubstituted alkyl groups in accordance with the present teachings include, but are not limited to, methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl, tert-butyl, sec-butyl, cyclobutyl, pentyl , cyclopentyl, hexyl, cyclohexyl and the like.

[0019] The term "alkenyl" refers to a substituted or unsubstituted, straight, branched or cyclic, unsaturated hydrocarbon chain that contains at least one double bond and, in some embodiments, from 2 to 24 carbon atoms. Representative unsubstituted alkenyl groups in accordance with the present teachings include, but are not limited to, ethenyl or vinyl (-CH=CH2), 1-propenyl, 2-propenyl or allyl (-CH2-CH=CH2), 1,3 -butadienyl (-CH=CHCH=CH2), 1-butenyl (-CH=CHCH2CH3), hexenyl, pentenyl, 1,3,5-hexatrienyl and the like. In some embodiments, cycloalkenyl groups have five to eight carbon atoms and at least one double bond. Representative cycloalkenyl groups in accordance with the present teachings include, but are not limited to, cyclohexadienyl, cyclohexenyl, cyclopentenyl, cycloeptenyl, cyclooctenyl, cyclohexadienyl, cycloheptadienyl, cyclooctatrienyl and the like.

[0020] The term "alkoxy" refers to a substituted or unsubstituted -O-alkyl group. Representative unsubstituted alkoxy groups in accordance with the present teachings include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy and the like.

[0021] The terms "siloxy" and "silyloxy" refer to oxygen groups substituted with silicon. The silicon-containing portion of the siloxy group may be substituted or unsubstituted. Representative siloxy groups in accordance with the present teachings include, but are not limited to, trimethylsilyloxy (-OSi(CH3)3), triethylsilyloxy (-OSi(CH2CH3)3), triisopropylsiloxy (-OSi(i-Pr)3, tert-butyldimethylsiloxy (-OSi(tert-Bu)(CH3)2) and the like.

[0022] The term "alkynyl" refers to a substituted or unsubstituted, straight, branched or cyclic unsaturated hydrocarbon chain containing at least one triple bond and, in some embodiments, from 2 to 20 carbon atoms.

[0023] The term "aryl" refers to a substituted or unsubstituted mono-, bi- or polycyclic aromatic ring system of 4-20 carbon atoms. Representative aryl groups in accordance with the present teachings include, but are not limited to, benzene, substituted benzene (e.g., toluene, xylenes, styrene), naphthalene, anthracene, biphenyl and the like.

[0024] The term "amino" refers to an unsubstituted or unsubstituted amino group (-NH2). The amine can be primary (-NH2), secondary (-NHRa) or tertiary (-NRaRb, where Ra and Rb are the same or different). Representative substituted amino groups in accordance with the present teachings include, but are not limited to, methylamino, dimethylamino, ethylamino, dimethylamino, 2-propylamino, 1-propylamino, di(n-propyl)amino, di(iso-propyl)amino, methyl-n-propylamino, tert-butylamino and the like.

[0025] The term "halogen" refers to fluorine, chlorine, iodine or bromine.

[0026] The term "heterocyclic" refers to a saturated, partially unsaturated or aromatic ring system containing from 3 to 24 carbon atoms (in some embodiments, 4 to 2 carbon atoms; in other embodiments 6 to 20 carbon atoms) and at least one heteroatom (in some embodiments 1 to 3 heteroatoms). The ring may be optionally substituted with one or more substituents. Furthermore, the ring may be mono-, bi- or polycyclic. As used herein, the term "heterocyclic" comprises the term "heteroaryl". Representative heteroatoms for ring inclusion include, but are not limited to, nitrogen, oxygen, and sulfur. Representative heterocyclic groups in accordance with the present teachings include, but are not limited to, aziridine, azirine, oxirane, oxirene, tyranne, thiyrene, diazirine, oxaziridine, dioxirane, azetidine, azete, oxetane, oxete, thiethane, groupet, diazetidine, dioxane , dioxette, dithiethane, dithiene, pyrrolidine, tetrahydrofuran, thiolane, imidazolidine, pyrazolidene, oxazolidine, isooxazolidine, thiazolidine, isothiazolidene, dioxolane, dithiolane, furazan, oxadiazole, dithiazole, tetrazole, piperidine, oxane, pyran, thiano, thiopyran, piperazine, diazines , morpholine, oxazine, thiomorpholine, thiazine, dioxane, dioxin, dithian, dithiine, tritiano, tetrazine, azepane, azepine, oxepane, oxepin, thiepane, thiepin, homopiperazine, diazepine, thiazepine, azocane, azocine, acridine, benzathiozoline, benzimidazole, benzofuran , benzothiapene, benzothiazole, benzothiophenyl, carbazole, crinoline, furan, imidazole, 1H-indazole, indole, isoindole, isoquinoline, isothiazole, oxazole, isoxazole, oxadiazoles (e.g. 1,2,3-oxadiazole), phenazine, phenothiazine, phenoxazine , phthalazine, pteridine, purine, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, quinazoline, quinoline, quinoxaline, thiazole, thiadiazoles (e.g. 1,3,4-thiadiazole), thiophene, triazine (e.g. 1, 3,5-triazine), triazoles (e.g. 1,2,3-triazole) and the like.

[0027] The term "substituted" refers to the optional attachment of one or more substituents to a backbone structure (e.g., an alkyl backbone, an alkenyl backbone, a heterocyclic backbone, etc.). Representative substituents for use in accordance with the present teachings include, but are not limited to, hydroxyl groups, amino (-NH2, NHRa, -NRaRb), oxy (-O-), carbonyl (-CO-), thiol, alkyl, alkenyl, alkynyl, alkoxy, halo, nitrile, nitro, aryl and heterocyclyl. The substituents may further optionally be substituted with 1-3 substituents. Examples of substituted substituents include, but are not limited to, carboxamide, alkylmercapto, alkylsulfonyl, alkylamino, dialkylamino, carboxylate, alkoxycarbonyl, alkylaryl, aralkyl, alkyleterocyclyl, heterocyclylaryl, haloalkyl and the like. The substituent must not substantially chemically interfere with the reaction of the invention (e.g., cross-react with reagents, terminate the reaction, or the like).

[0028] It should be understood that elements and characteristics of the various representative modalities described below can be combined in different ways to produce new modalities that also fall within the scope of the present teachings.

[0029] By way of general introduction, a heat transfer fluid concentrate in accordance with the present teachings includes (a) a freezing point depressant, water or a combination thereof; (b) an organophosphate; (c) a carboxylic acid or a salt thereof; and (d) a component selected from the group consisting of an alkaline earth metal ion, an alkali metal ion, a transition metal ion, an inorganic phosphate, molybdate ion, nitrate ion, nitrite ion, an azole compound, a copper or copper alloy corrosion inhibitor, a silicate, a silicate stabilizer, a water-soluble polymer and combinations thereof.

[0030] In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings optionally further includes one or a plurality of additional components selected from the group consisting of a phosphonate, a phosphinate, a colorant, a biocide, an antifoam , a surfactant, a dispersant, a particle anti-deposition agent, a wetting agent, an additional corrosion inhibitor and combinations thereof. In some embodiments, the pH of the heat transfer fluid concentrate according to the present teachings at 50% concentration is between about 6.8 and about 10.0.

[0031] Heat transfer fluid concentrates in accordance with the present teachings include a freezing point depressant, water or a combination thereof. Representative freezing point depressants suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, alcohol and alcohol mixtures (e.g., monohydric alcohols, polyhydric alcohols, and mixtures of of the same). Representative alcohols for use as freezing point depressants include, but are not limited to, methanol, ethanol, propanol, butanol, furfurol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethoxylated furfuryl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, glycerol, glycerol-1,2-dimethyl ether, glycerol-1,3-dimethyl ether, glycerol monoethylether, sorbitol, 1 ,2,6-hexanetriol, trimethylolpropane, alkoxy alkanols (e.g., methoxyethanol), and the like, and combinations thereof.

[0032] In some embodiments, the freezing point depressant comprises an alcohol which, in some embodiments, is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, glycerol and a combination thereof . In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings contains a glycol freezing point depressant. Freezing point depressant concentration may vary depending on the application. By way of example, in some embodiments, the concentration of the freezing point depressant may vary from about 0% by weight to about 60% by weight based on the total weight of the heat transfer fluid concentrate ( for example, from about 0% by weight to about 50% by weight, from about 5% by weight to about 40% by weight, or from about 11% by weight to approximately 25% by weight). In other embodiments, the concentration of the freezing point depressant can range from about 1% by weight to about 99% by weight, in some embodiments from about 10% by weight to about 99, 9% by weight, based on the total weight of the heat transfer fluid concentrate (e.g., from about 30% by weight to about 99.5% by weight or from about 40% by weight by weight to about 99% by weight). In some embodiments, the concentration of the freezing point depressant varies from about 15% by weight to about 99% by weight based on the total weight of the heat transfer fluid concentrate. In other embodiments, the concentration of the freezing point depressant varies from about 20% by weight to about 98% by weight based on the total weight of the heat transfer fluid concentrate. In additional embodiments, the concentration of the freezing point depressant varies from about 20% by weight to about 96% by weight based on the total weight of the heat transfer fluid concentrate.

[0033] Heat transfer fluid concentrates in accordance with the present teachings may include water in addition to, or as an alternative to, a freezing point depressant. Ready-to-use heat transfer fluids derived from heat transfer fluid concentrates (e.g., through dilution) typically contain water. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings that contains a freezing point depressant can be diluted with water to a 30 vol% solution. at 60% vol.

[0034] The type of water used in accordance with the present teachings is not restricted. However, in some embodiments, the water used in a heat transfer fluid concentrate and/or a heat transfer fluid in accordance with the present teachings includes deionized water, demineralized water, softened water, or a combination thereof. In some embodiments, a water hardness due to CaCO3 is less than about 20 ppm. In other embodiments, an electrical conductivity of water is less than about 300 μS/cm. In further embodiments, a water hardness due to CaCO3 is less than about 20 ppm and an electrical conductivity of the water is less than about 30 μS/cm. The amount of water may vary depending on the application. By way of example, the concentration of water may vary from about 0.1% by weight to about 90% by weight based on the total weight of the heat transfer fluid concentrate (e.g., from from about 0.5% by weight to about 70% by weight or from about 1% by weight to about 60% by weight).

[0035] Heat transfer fluid concentrates in accordance with the present teachings include one or more organophosphates (also known as phosphate esters). In some embodiments, an organophosphate for use in accordance with the present teachings has the following structure (1): wherein R1, R2 and R3 are each independently hydrogen, an optionally substituted heteroatom-containing alkyl, an optionally substituted heteroatom-containing alkenyl, an optionally substituted carbonyl-containing alkyl, an optionally substituted carbonyl-containing alkenyl or an optionally substituted portion selected from the group consisting in alkyl, alkenyl, aryl, phosphono, phosphine, alkylamino, amino and combinations thereof. For some embodiments in which an organophosphate R group (i.e., R1, R2, and/or R3) contains one or more heteroatoms, the one or more heteroatoms may form an ether bond (e.g., -COC-), a sulfide bond. (-CSC), an amino bond (-CNC) or a combination thereof.

[0036] Representative organophosphates for use in accordance with the present teachings include, but are not limited to, ethylene glycol phosphate, 1,2,3-propanetriol phosphate (CAS No. 12040-65-2); a phosphate polyether ester; a C6 - C12 alkyl alcohol ethoxylated phosphoric acid (CAS No.: 68921-24-4); an alkali metal salt of cresyl ethoxylate phosphate ester (CAS No.: 66057-30-5); potassium cresyl phosphate (CAS No.: 37281-48-4); octylphenoxypolyethoxyethyl phosphate; octylphenoxy polyethyl phosphate, olyethylene glycol mono(octylphenyl) ether phosphate; alkali metal salts of alkylphenoxypolethoxyethyl phosphoric acid having a formula R-phenyl(CH2CH2O)xphosphate wherein R is hydrogen or C1-C20 alkyl (in some embodiments, C1-C2) and x is equal to 1 to 30 (in some embodiments, 2 to 10); alkyl or aryl acid phosphates, such as isooctyl acid phosphate; 2-ethylhexyl acid phosphate, amyl acid phosphate, amyl dihydrogen phosphate, diamyl hydrogen phosphate, butyl acid phosphate and/or similar; and combinations thereof.

[0037] Representative phosphate esters suitable for use in accordance with the present teachings are available from many suppliers including, but not limited to, Dow Chemical Company (Midland, MI), Stepan Company (Northfield, IL), Solvay S.A./Rhodia Inc .(Brussels, Belgium), Ashland Inc. (Covington, KY), Clariant Corporation (Muttenz, Switzerland), PCC Chemax Inc. (Piedmont, SC), IsleChem LLC (Grand Island, NY), and Lakeland Laboratories Limited (Manchester, England ).

[0038] In some embodiments, the organophosphate used in accordance with the present invention may be selected from the group consisting of polyether phosphate esters or alcohol phosphate esters including, but not limited to (a) Triton™ H-66 surfactants, Triton™ H-55, Triton™ QS-44 and/or Triton™ XQS-20 from Dow Chemical Company; (b) Rhodafac® H-66 or potassium salt of cresyl ethoxylate phosphate ester (CAS No. 66057-30-5), Rhodafac H-66-E or potassium salt of aromatic ethoxylate phosphate esters, Rhodafac HA-70 or polyoxyethylene phenyl ester phosphate acid form (CAS No. 39464-70-5), Rhodafac PA 23 or ethoxylated fatty alcohol phosphate ester (CAS No. 68585-36-4) and/or Rhodafac LO/529-E or ethoxylated alkylphenol phosphate sodium salt (CAS No. 68954-84-7) from Rhodia; (c) Cedephos FA-600 containing C6-C12 alkyl alcohol ethoxylate phosphoric acids (CAS No. 68921-24-4, CAL alt No. 68130-47-2) and/or MERPOL A (alcohol phosphate) of Stepan Company: (d) Chemfac NF-100 (98% phosphoric acids, esters with ethylene glycol, CAS No. 68553-96-8) or ethylene glycol phosphate, Chemfac NA-350 or 1,2,3-propanetriol phosphate (CAS No. 12040-65-2), as the main component in Chemfac NA-350), Chemfac PB-106K (polyoxyethylene decyl phosphate, potassium salt or poly(oxy-1,2-ethanediyl), alpha -isodecyl-omega-hydroxy-phosphate, potassium salt, CAS No. 68071-17-0), Chemfac PB-184 (POE oleyl phosphate or poly(oxy-1,2-ethanediyl), alpha-9- octadecenyl- omega-hydroxy-(Z)-, phosphate, CAS No. 39464-69-2), Chemfac PF-636 (poly(oxy-1,2-ethanediyl), alpha-hydroxy-omega-hydroxy, phosphate , CAS No. 9056-42-2), Chemfac PB-264 (POE ether phosphate or poly(oxy-1,2-ethanediyl), alpha-hydroxy-omega-hydroxy, mono-C12-C14- ethers alkyl, phosphates, CAS No. 68511-37-5), Chemfac NC-096 (POE (6) nonyl phenol phosphate or poly(oxy-1,2-ethanediyl), alpha-(nonylphenyl)-omega-hydroxy , branched, phosphates, CAS No. 68412-53-3), Chemfac NB-041 (POE aliphatic phosphate ester), Chemfac NB-042 (POE aliphatic phosphate ester), Chemfac 126 (POE aliphatic phosphate ester), Chemfac NB-159 (POE aliphatic phosphate ester), Chemfac NC-006E (POE aliphatic phosphate ester), Chemfac NC-0910 (aliphatic phosphate ester), Chemfac PB-082 (POE aliphatic phosphate ester), Chemfac PB-104 (aliphatic phosphate ester), Chemfac PB-109, Chemfac PB-133, Chemfac PB-135, Chemfac PB-136, Chemfac PB-139, Chemfac PB-253, Chemfac PC-006, Chemfac PC-099, Chemfac PC- 188, Chemfac PD-600, Chemfac PD-990 and/or Chemfac PF-623 from PCC Chemax Inc.; (e) phosphate alcohols such as PA 100, PA 800, PA 800K and PA 801 from Lakeland Laboratories, Ltd.; (f) phosphate alcohol ethoxylates such as PAE 802, PAE 106, PAE 126, PAE 136, PAE 147, PAE 176, PAE 185 and PAE 1780 from Lakeland Laboratories Ltd.; (g) phosphate phenol ethoxylate such as PPE 604, PPE 604K, PPE 154, PPE 156, PPE 159 and PPE 1513 from Lakeland Laboratories Ltd.; (h) and/or similar; and (i) combinations thereof.

[0039] In some embodiments, organophosphates for use in accordance with the present teachings include alkyl and aryl acid phosphates. Representative alkyl or aryl acid phosphates that may be used in accordance with the present teachings include, but are not limited to, amyl acid phosphate, n-butyl acid phosphate, methyl acid phosphate, phenyl acid phosphate, amyl acid phosphate, 2- ethyl hexyl, dimethyl acid phosphate, isooctyl acid phosphate and/or similar and combinations thereof. Monoalkyl/aryl acid phosphates, dialkyl/aryl acid phosphates or a combination thereof can be used in accordance with the present teachings.

[0040] In some embodiments, organophosphates for use in accordance with the present teachings include ethylene glycol phosphate (e.g., Chemfac NF-100), polyether phosphate ester (e.g., Triton H-66) or a combination thereof. Suitable polyether phosphate esters for use in accordance with the present teachings include, but are not limited to, those described in United States Patent Nos. 3,235,627; 3,462,520; 3,294,693; and 3,462,520.

[0041] The amount of organophosphate may vary depending on the application. By way of example, the concentration of the one or more organophosphates may vary from about 0.0025% by weight to about 10% by weight based on the total weight of the heat transfer fluid concentrate (e.g., from about 0.005% by weight to about 5% by weight, from about 0.01% by weight to about 3% by weight, from about 0.05% by weight to about 2% by weight or from about 0.05% by weight to about 0.5% by weight. Within this range, the amount may be greater than or equal to about 0.005% by weight, and in In some embodiments, greater than or equal to about 0.001%. Also within this range, the amount may be less than or equal to about 1% by weight, and in some embodiments, less than or equal to about 0. .5% by weight.

[0042] Heat transfer fluid concentrates in accordance with the present teachings include one or a plurality of carboxylates. As used herein, the term "carboxylate" is inclusive of carboxylic acid, salts thereof, and combinations of one or more carboxylic acids and one or more carboxylic acid salts. Carboxylic acid salts suitable for use include alkali metal salts (such as lithium, sodium and potassium, etc.) and alkaline earth metal salts (such as calcium, magnesium and strontium, etc.). The carboxylate may include a single or multiple carboxyl group and may be linear or branched. It is expressly understood that combinations of carboxylates may be used and such combinations are comprised by the terms "carboxylate" and "carboxylic acid". In some embodiments, a carboxylate according to the present teachings has from 4 to 24 carbon atoms (e.g., 4 to 22 carbon atoms). In other embodiments, a carboxylate according to the present teachings has from 6 to 20 carbon atoms. The carboxylate can be aliphatic, aromatic, or a combination of both. In some embodiments, the carboxylic acid is a C6 to C20 aliphatic or aromatic mono- or dibasic carboxylic acid and/or an alkali metal salt thereof. In some embodiments, a carboxylate according to the present teachings consists of carbon, hydrogen and oxygen and is free of non-oxygen heteroatoms. Representative aliphatic carboxylates for use in accordance with the present teachings include, but are not limited to, 2-ethyl hexanoic acid, hexanoic acid, heptanoic acid, octanoic acid, neodecanoic acid, decanoic acid, nonanoic acid, isoeptanoic acid, dodecanoic acid, sebacic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, dodecanedioic acid and/or similar, and combinations thereof. Representative aromatic carboxylates include, but are not limited to, benzoic acid, toluic acid (methylbenzoic acid), tert-butyl benzoic acid, alkoxy benzoic acid (e.g., methoxybenzoic acid, such as o-, p-, or m-anisic acid) , salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, phenylacetic acid, mandelic acid, 1,2,4-benzenetricarboxylic acid and/or similar; and combinations thereof.

[0043] In some embodiments, the carboxylate used in a heat transfer fluid concentrate in accordance with the present teachings includes a plurality of carboxylates. In some embodiments, the carboxylate includes an aliphatic monocarboxylate, an aliphatic dicarboxylate, an aromatic monocarboxylate, an aromatic dicarboxylate, or a combination thereof. In some embodiments, the carboxylate includes one or a plurality of C6-C20 carboxylates, and each of the one or plurality of C6-C20 carboxylates is individually selected from the group consisting of an aliphatic monocarboxylate, an aliphatic dicarboxylate, an aromatic monocarboxylate, an aromatic dicarboxylate and a combination thereof. In some embodiments, the carboxylate includes neodecanoic acid and at least one additional aliphatic or aromatic mono- or dibasic carboxylic acid. In some embodiments, the carboxylate includes 2-ethyl hexanoic acid, neodecanoic acid, or a combination thereof.

[0044] The carboxylate concentration may vary depending on the application. In some embodiments, the carboxylate is present in an amount of from about 0.1% by weight to about 25% by weight, in some embodiments about 1% by weight to about 10% by weight, based on in the total weight of the heat transfer fluid concentrate. Within this range, the amount may be greater than or equal to about 1.5% by weight and, in some embodiments, greater than or equal to about 2% by weight. Also within this range, the amount may be less than or equal to about 7% by weight and, in some embodiments, less than or equal to about 5% by weight.

[0045] Heat transfer fluid concentrates in accordance with the present teachings include one or a combination of more than one components selected from the following list: a component selected from the group consisting of an alkaline earth metal ion, an alkali metal ion , a transition metal ion, an inorganic phosphate, molybdate ion, nitrate ion, nitrite ion, an azole compound, a copper and copper alloy corrosion inhibitor, a silicate, a silicate stabilizer, a soluble polymer in water and combinations thereof. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings may specifically exclude one or more of the components mentioned above (e.g., be substantially "free" of one or more of the components mentioned above).

[0046] In accordance with the present teachings, heat transfer fluid concentrates may include at least one metal ion (e.g., a metal ion derived from a water-soluble metal salt, an insoluble metal compound, or poorly soluble in water, a metal oxide and/or similar and combinations thereof). In some embodiments, the metal ion may be derived from a soluble alkaline earth metal salt (e.g., a calcium salt, a magnesium salt, and/or a strontium salt), an alkaline earth metal compound (e.g., a calcium compound, a magnesium compound and/or a strontium compound), an alkaline earth metal oxide (e.g. calcium oxide, magnesium oxide and/or strontium oxide, a water-soluble alkali metal salt (e.g. e.g., a lithium salt), an alkali metal compound (e.g., a lithium compound), an alkali metal oxide (e.g., lithium oxide), a transition metal salt (e.g., a zinc), a transition metal compound (e.g., a zinc compound), a transition metal oxide (e.g., zinc oxide) and/or a combination thereof.

[0047] In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings includes one or more water-soluble alkaline earth metal salts, which will produce an alkaline earth metal ion (in some embodiments, Ca2+, Mg2+ and/or or Sr2+) when dissolving in water. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings includes one or more water-soluble alkaline earth metal oxides, which will produce an alkaline earth metal ion in the heat transfer fluid (in some embodiments, Ca2+, Mg2+ and/or Sr2+) when mixed with other acidic components of heat transfer fluids (for example, carboxylic acids and/or organophosphates). In some embodiments, the concentration of the alkaline earth metal ion derived from one or more alkaline earth metal salts and/or one or more alkaline earth metal oxides is in the range of about 0 mg/L to about 200 mg/L (i.e. , up to about 200 mg/L) in the heat transfer fluid concentrate.

[0048] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include a water-soluble alkaline earth metal salt and/or an alkali metal compound that provides a source of calcium ions. In some embodiments, the calcium ions are derived from one or a plurality of calcium compounds or salts (e.g., one or more water-soluble calcium salts). In some embodiments, the calcium ions are derived from one or a plurality of water-soluble calcium salts that are configured to at least partially dissociate in an aqueous solution at room temperature. In some embodiments, the one or plurality of calcium salts are configured to produce between about 1 and about 60 mg/L of calcium ions (Ca2+) in the heat transfer fluid concentrate upon dissolution.

[0049] Calcium compounds for use in accordance with the present teachings include, but are not limited to, inorganic calcium compounds and calcium salts of organic acids containing one or a plurality of carboxylic acid groups. Representative organic calcium compounds include, but are not limited to, calcium hydroxide, calcium oxide, calcium molybdate, calcium vanadate, calcium tungstate, calcium perchlorate, calcium chloride, and/or the like, hydrates of any of the salts mentioned above, and combinations thereof. Representative calcium salts of organic acids include, but are not limited to, calcium acetate, calcium formate, calcium propionate, calcium polymaleate, calcium polyacrylate, calcium lactate, calcium gluconate, calcium glycolate, calcium glucoheptonate , calcium citrate, calcium tartrate, calcium glucarate, calcium succinate, calcium hydroxysuccinate, calcium adipate, calcium oxalate, calcium malonate, calcium sulfamate, calcium salts of aliphatic tricarboxylic acid, calcium salts of acid aliphatic tetracarboxylic acid, and/or similar, hydrates of any of the calcium salts mentioned above, and combinations thereof.

[0050] In some embodiments, the calcium compound may be a calcium salt formed between calcium ions and a phosphate or a phosphinate, such as calcium salts-PBTC (where PBTC is 2-phosphonobutane-1,2,4 acid -tricarboxylic acid), calcium salts-HEDP (where HEDP is 1-hydroxyethane-1,1-diphosphonic acid), calcium salts-HPA (where HPA is hydroxyphosphonoacetic acid or 2-hydroxyphosphonoacetic acid), acid salts calcium phosphonosuccinic acid, calcium-PSO salts (where PSO are mixtures of mono-, bis- and oligomeric phosphonosuccinic acid adduct as described in U.S. Patent No. 6,572,789 B1) and/or the like, and combinations thereof.

[0051] The concentration of calcium ion (Ca2+) may vary depending on the application. In some embodiments, one or more calcium compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. As used herein, the term "soluble" refers to a degree of dissolution such that no particulate matter remains visible to the naked eye. In some embodiments, the Ca2+ concentration in a heat transfer fluid concentrate in accordance with the present teachings is between about 0 mg/mL and about 200 mg/L (i.e., up to about 200 mg/L). . In other embodiments, the Ca 2+ concentration in the heat transfer fluid concentrate in accordance with the present teachings is between about 0.1 mg/L and about 150 mg/L, between about 0.1 mg/L and about 80 mg/L, between about 0.2 mg/L and about 60 mg/L, 0.2 mg/L and about 40 mg/L or between about 1 mg/L and about 60 mg /L. In additional embodiments, the calcium ion concentration is between about 3 mg/mL and about 40 mg/L. In still further embodiments, the calcium ion concentration is between about 4 mg/L and about 30 mg/L.

[0052] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include a water-soluble alkaline earth metal salt and/or an alkaline earth metal compound that provides a source of magnesium ions. In some embodiments, the magnesium ions are derived from one or a plurality of magnesium compounds or salts (e.g., one or more water-soluble magnesium salts). In some embodiments, the magnesium ions are derived from one or a plurality of water-soluble magnesium salts that are configured to at least partially dissociate in an aqueous solution at room temperature. In some embodiments, the one or plurality of magnesium salts are configured to produce up to about 150 mg/mL of magnesium ions in the heat transfer fluid concentrate upon dissolution based on the total weight of the heat transfer fluid concentrate. of heat.

[0053] Magnesium compounds for use in accordance with the present teachings include, but are not limited to, inorganic magnesium compounds and magnesium salts of organic acids containing one or a plurality of carboxylic acid groups. Representative inorganic magnesium compounds include, but are not limited to, magnesium molybdate, magnesium hydroxide, magnesium oxide, magnesium tungstate, magnesium sulfate, magnesium perchlorate, magnesium chloride, magnesium vanadate, and/or the like. hydrates of any of the magnesium salts mentioned above and combinations thereof. Magnesium salts representative of organic acids include, but are not limited to, magnesium formate, magnesium acetate, magnesium propionate, magnesium polyacrylate, magnesium polymaleate, magnesium lactate, magnesium gluconate, magnesium glycolate, magnesium glucoheptonate , magnesium citrate, magnesium tartrate, magnesium glucarate, magnesium succinate, magnesium hydroxysuccinate, magnesium adipate, magnesium oxalate, magnesium malonate, magnesium sulfamate, and/or similar, and combinations thereof.

[0054] In some embodiments, the magnesium compound may be a magnesium salt formed between magnesium ions and a phosphonate or a phosphinate, such as magnesium salts-PBTC (where PBTC is 2-phosphonobutane-1,2,4 acid -tricarboxylic acid), magnesium salts-HEDP (where HEDP is 1-hydroxyethane-1,1-diphosphonic acid), magnesium salts-HPA (where HPA is hydroxyphosphonoacetic acid or 2-hydroxyphosphonoacetic acid), acid salts magnesium phosphonosuccinic acid, magnesium-PSO salts (where PSO are mixtures of mono-, bis- and oligomeric phosphinosuccinic acid adduct as described in U.S. Patent No. 6,572,789 B1), and/or similar, hydrates of the salts mentioned above, or combinations thereof.

[0055] The magnesium ion concentration may vary depending on the application. In some embodiments, one or more magnesium compounds present in the heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the magnesium ion (Mg2+) concentration in the heat transfer fluid concentrate in accordance with the present teachings is between about 0 mg/mL and about 200 mg/L (i.e., up to about 200 mg/L). In other embodiments, the concentration of Mg2+ in a heat transfer fluid concentrate in accordance with the present teachings is between about 0 mg/L and about 150 mg/L (i.e., up to about 150 mg/L). , between about 1 mg/L and about 100 mg/L, between about 0.1 mg/L and about 80 mg/L, between about 0.2 mg/L and about 40 mg/L, or between about 1 mg/L and about 50 mg/L (e.g., 1 mg/L and 25 mg/L). In additional embodiments, the magnesium ion concentration is between about 3 mg/L and about 80 mg/L. In other embodiments, the magnesium ion concentration is between about 2 mg/L and about 35 mg/L. In additional embodiments, the magnesium ion concentration is between about 4 mg/L and about 30 mg/L.

[0056] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include a water-soluble alkaline earth metal salt and/or an alkaline earth metal compound that provides a source of strontium ions. In some embodiments, the strontium ions are derived from one or a plurality of strontium compounds or salts (e.g., one or more water-soluble strontium salts). In some embodiments, the strontium ions are derived from one or a plurality of water-soluble strontium salts that are configured to at least partially dissociate in an aqueous solution at room temperature. In some embodiments, the one or plurality of strontium salts are configured to produce up to about 50 mg/L of strontium ions in the heat transfer fluid concentrate upon dissolution based on the total weight of the heat transfer fluid concentration. of heat.

[0057] Strontium compounds for use in accordance with the present teachings include, but are not limited to, inorganic strontium compounds and strontium salts of organic acids containing one or a plurality of carboxylic acid groups. Representative inorganic strontium compounds include, but are not limited to, strontium hydroxide, strontium oxide, strontium chloride, strontium perchlorate, strontium nitrate, strontium iodide, strontium sulfate, strontium borate, strontium phosphate, di -strontium hydrogen phosphate, strontium molybdate, strontium tungstate, strontium titanate, and/or similar, hydrates of any of the strontium salts mentioned above, and combinations thereof. A strontium compound may also be a strontium salt formed between a strontium ion and an organic acid containing one or more carboxylic acid groups or one or more phosphonic acid groups or one or more phosphinic acid groups or a combination of these groups. functional. Strontium salts representative of organic acids include, but are not limited to, strontium formate, strontium acetate, strontium propionate, strontium butyrate, strontium polyacrylate, strontium lactate, strontium polymaleate, strontium gluconate, strontium glycolate , strontium glucoheptonate, strontium citrate, strontium tartrate, strontium glucarate, strontium succinate, strontium hydroxysuccinate, strontium adipate, strontium oxalate, strontium malonate, strontium sulfamate, strontium sebacate, strontium benzoate, f thallate strontium, strontium salicylate, strontium salts-PBTC (where PBTC is 2-phosphonobutane-1,2,4-tricarboxylic acid), strontium salts-HEDP (where HEDP is 1-hydroxyethane-1,1-diphosphonic acid) , strontium-HPA salts (where HPA is hydroxyphosphonoacetic acid or 2-hydroxy phosphonoacetic acid), strontium phosphonosuccinic acid salts, strontium-PSO salts (where PSO is mono-, bis- and oligomeric phosphinosuccinic acid adduct mixtures), or hydrates of these salts, or combination of the above strontium compounds.

[0058] The strontium ion concentration may vary depending on the application. In some embodiments, one or more strontium compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the strontium (Sr2+) ion concentration in a heat transfer fluid concentrate in accordance with the present teachings is between about 0 mg/L and about 50 mg/L (i.e., up to about 50 mg/L). In other embodiments, the concentration of Sr2+ in a heat transfer fluid concentrate in accordance with the present teachings is between about 0.1 mg/L and about 40 mg/L, between about 0.5 mg/L and about 30 mg/L, between about 1 mg/L and about 25 mg/L, between about 2 mg/L and about 20 mg/L, or between about 4 mg/L and about 16 mg /L.

[0059] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include one or a plurality of inorganic phosphates. The inorganic phosphate used in accordance with the present teachings is configured to generate phosphate ions upon dissolution in an aqueous solution. Representative inorganic phosphates for use in accordance with the present teachings include, but are not limited to, orthophosphate such as phosphoric acid, alkali metal orthophosphate (e.g., sodium orthophosphate, potassium orthophosphate, etc.), other metal phosphate salts. water-soluble alkaline, and/or similar, and combinations thereof. In some embodiments, an inorganic phosphate for use in accordance with the present teachings is selected from the group consisting of phosphoric acid, sodium orthophosphate, potassium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium polyphosphate, potassium polyphosphate, sodium hexametaphosphate. sodium, potassium hexametaphosphate, and/or similar, and combinations thereof. In some embodiments, the inorganic phosphate includes phosphoric acid and/or one or more additional orthophosphates including, but not limited to, alkali metal orthophosphate and/or other water-soluble alkali metal phosphate salts.

[0060] The concentration of inorganic phosphate may vary depending on the application. In some embodiments, the phosphate ion concentration in a heat transfer fluid concentrate in accordance with the present teachings ranges from about 0.00% by weight to about 5% by weight (i.e., up to about 5% by weight) based on the total weight of the heat transfer fluid. In other embodiments, the phosphate ion concentration ranges from about 0.01 wt% to about 1 wt% based on the total weight of the heat transfer fluid. In some embodiments, inorganic phosphate may be present in the heat transfer fluid concentrate in an amount between 0.10% by weight and about 0.60% by weight based on the total weight of the heat transfer fluid concentrate. . Within this range, the amount may be greater than or equal to about 0.11% by weight and, in some embodiments, greater than or equal to about 0.12% by weight. Also within this range, the amount may be less than or equal to about 0.45% by weight and, in some embodiments, less than or equal to about 0.40% by weight.

[0061] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include lithium ions. In some embodiments, lithium ions are derived from one or a plurality of lithium compounds or salts (e.g., one or more water-soluble lithium salts). In some embodiments, the lithium ions are derived from one or a plurality of water-soluble lithium salts that are configured to at least partially dissociate in an aqueous solution at room temperature. In some embodiments, the one or plurality of lithium salts are configured to produce lithium ion at a concentration ranging from about 0 ppm to about 6000 ppm (i.e., up to about 6000 ppm) in the concentrate. heat transfer fluid when dissolving based on the total weight of the heat transfer fluid concentration.

[0062] Lithium compounds for use in accordance with the present teachings include, but are not limited to, inorganic lithium compounds and lithium salts of organic acids containing one or a plurality of carboxylic acid groups. Representative inorganic lithium compounds include, but are not limited to, lithium hydroxide, lithium oxide, lithium phosphate, lithium borate, lithium perchlorate, lithium sulfate, lithium molybdate, lithium vanadate, lithium tungstate, lithium carbonate of lithium, and/or similar, hydrates of any of the lithium salts mentioned above, and combinations thereof. Lithium salts representative of organic acids include, but are not limited to, lithium acetate, lithium benzoate, lithium polyacrylate, lithium polymaleate, lithium lactate, lithium citrate, lithium tartrate, lithium gluconate, lithium glucoheptonate , lithium glycolate, lithium glucarate, lithium succinate, lithium hydroxyl succinate, lithium adipate, lithium oxalate, lithium malonate, lithium sulfamate, lithium formate, lithium propionate, and/or the like, and combinations thereof same

[0063] In some embodiments, the lithium compound may be a lithium salt formed between lithium ions and a phosphonate or phosphinate, such as lithium-PBTC salts (where PBTC is 2-phosphonobutane-1,2,4- triacarboxylic acid), lithium-HEDP salts (where HEDP is 1-hydroxyethane-1,1-diphosphonic acid), lithium-HPA salts (where HPA is hydroxyphosphonoacetic acid or 2-hydroxyphosphonoacetic acid), phosphonosuccinic acid salts lithium, lithium-PSO salts (where PSO are oligomeric phosphinosuccinic acid adduct mixtures as described in U.S. Patent No. 6,572,789 B1), and/or similar, hydrates of the salts mentioned above, or combinations thereof.

[0064] The lithium ion concentration may vary depending on the application. In some embodiments, one or more lithium compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the lithium ion (Li+) concentration in the heat transfer fluid concentrate in accordance with the present teachings is between about 0 ppm and about 6000 ppm (e.g., between about 0 ppm and about 5000 ppm) based on the total weight of the heat transfer fluid concentrate. Within this range, the titanium ion concentration may be less than about 4000 ppm and, in some embodiments, less than equal to about 3000 ppm. Also within this range, the lithium ion concentration may be greater than or equal to about 50 ppm, and in some embodiments, greater than or equal to about 100 ppm, and in other embodiments greater than or equal to about of 200 ppm.

[0065] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include zinc ions. In some embodiments, the zinc ions are derived from one or a plurality of zinc compounds or salts (e.g., one or more water-soluble zinc salts). In some embodiments, the zinc ions are derived from one or a plurality of water-soluble zinc salts that are configured to at least partially dissociate in an aqueous solution at room temperature. In some embodiments, the one or plurality of zinc salts are configured to produce zinc ion at a concentration ranging from about 0 ppm to about 50 ppm (i.e., up to about 50 ppm) in the concentrate. heat transfer fluid when dissolving based on the total weight of the heat transfer fluid concentrate. Zinc compounds for use in accordance with the present teachings include, but are not limited to, inorganic zinc compounds and zinc salts of organic acids containing one or a plurality of carboxylic acid groups. Representative inorganic zinc compounds include, but are not limited to, zinc hydroxide, zinc oxide, zinc nitrate, zinc sulfate, zinc chloride, zinc perchlorate, zinc chlorate, zinc bromide, zinc bromate, iodide of zinc, and/or similar, hydrates of any of the zinc salts mentioned above, and combinations thereof. A zinc compound suitable for use may also be a zinc salt formed between a zinc ion and an organic acid containing one or more carboxylic acid groups, one or more phosphonic acid groups, one or more phosphinic acid groups, or a combination of these functional groups. Representative organic zinc salts of organic acids include, but are not limited to, zinc formate, zinc acetate, zinc propionate, zinc butyrate, zinc lactate, zinc glycolate, zinc gluconate, zinc glueptonate, zinc malonate, zinc, zinc succinate, zinc glucarate, zinc hydroxysuccinate, zinc citrate, zinc benzoate, zinc phthalate, zinc adipate, zinc salicylate, zinc polyacrylate, zinc polymaleate, zinc salts-PBTC (where PBTC is 2-phosphonobutane-1,2,4-tricarboxylic acid), zinc salts-HEDP (where HEDP is 1-hydroxyethane-1,1-diphosphonic acid or 1-hydroxyethylidene-1,1-diphosphonic acid), zinc salts -HPA (where HPA is hydroxyphosphonoacetic acid or 2-hydroxy phosphonoacetic acid), zinc phosphonosuccinic acid salts, zinc phosphinosuccinic acid salts, zinc-PSO salts (where PSO are mono-, bis - and oligomeric), and/or similar, hydrates of the salts mentioned above, or combinations thereof.

[0066] The zinc ion concentration may vary depending on the application. In some embodiments, one or more zinc compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the zinc ion (Zn2+) concentration in a heat transfer fluid concentrate in accordance with the present teachings is between about 0 mg/mL and about 50 mg/mL (i.e., up to about 50 mg/L). In other embodiments, the concentration of Zn2+ in a heat transfer fluid concentrate in accordance with the present teachings is between about 0.1 mg/L and about 40 mg/L, between about 0.5 mg/L and about 30 mg/L, between about 1 mg/L and about 25 mg/L, between about 2 mg/L and about 20 mg/L, or between about 4 mg/L and about 16 mg /L.

[0067] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include one or more nitrates. In some embodiments, the nitrate ions are derived from one or a plurality of nitrate salts (e.g., one or more water-soluble nitrate salts). Representative nitrates for use in accordance with the present teachings include, but are not limited to, alkali metal nitrates and alkaline earth metal nitrates, such as sodium nitrate, potassium nitrate, lithium nitrate, calcium nitrate, magnesium nitrate, strontium nitrate and/or similar, hydrates of the salts mentioned above or combinations thereof. Representative nitrates for use in accordance with the present teachings also include, but are not limited to, alkaline earth metal nitrates, such as cerium(IV) nitrate, cerium(III) nitrate, and other rare earth metal nitrates (e.g., Sc, Y, La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and Yb), and/or similar, hydrates of the salts mentioned above, or combinations thereof.

[0068] The nitrate ion concentration may vary depending on the application. In some embodiments, one or more nitrate compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the nitrate compound is present in an amount of from 0% by weight to about 4% by weight (i.e., up to about 4% by weight), in some embodiments about 0% by weight. to about 1% by weight (i.e., up to about 1% by weight), in some embodiments, about 0% by weight to about 0.5% by weight (i.e., up to about 0.5% by weight) based on the total weight of the heat transfer fluid concentrate.

[0069] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include one or more nitrites. In some embodiments, the nitrite ions are derived from one or a plurality of nitrite salts (e.g., one or more water-soluble nitrite salts). Representative nitrites for use in accordance with the present teachings include, but are not limited to, alkali metal nitrites and alkaline earth metal nitrites, such as sodium nitrite, potassium nitrite, lithium nitrite, calcium nitrite, magnesium nitrite, strontium nitrite, and/or similar, hydrates of the salts mentioned above, or combinations thereof. Representative nitrites for use in accordance with the present teachings also include, but are not limited to, rare earth metal nitrites, such as lanthanum(III) nitrate, and other rare earth metal nitrites (e.g., Sc, Y , Ce, Nd, Sm, Eu, Gd, Dy, Er and Yb, etc.), and/or similar, hydrates of the salts mentioned above, or combinations thereof.

[0070] The nitrite ion concentration may vary depending on the application. In some embodiments, one or more nitrite compounds present in a heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the nitrate compound is present in an amount of from about 0% by weight to about 4% by weight (i.e., up to about 4% by weight), in some embodiments about 0%. by weight to 1% by weight (i.e., up to about 1% by weight), in some embodiments, about 0% by weight to 0.5% by weight (i.e., up to about 0.5% by weight). ) based on the total weight of the heat transfer fluid concentrate.

[0071] To protect iron alloy cylinder liners from cavitation corrosion in some heavy-duty diesel engines, nitrite can be used alone or in combination with molybdate ions in coolants designed for use in heavy-duty engines. The use of nitrite-containing coolants for heavy-duty engines is widespread as it is required by some Original Equipment Manufacturers (i.e., engine or truck manufacturers) or by standard coolant specification requirements or recommendations (e.g., ASTM D6210 , Chinese Motor Vehicle Engine Coolant Standard GB 29743-2013 and Truck Maintenance Council Recommended Practice RP329). Based on conventional recommendations for using nitrite to protect iron alloy cylinder linings from cavitation corrosion, heavy-duty antifreezes/coolants may contain nitrite ions in the following concentration ranges. Heavy-duty antifreeze/coolant concentrate products may contain (1) at least 2400 ppm nitrite as NO2- or (2) a minimum combined concentration of 1560 ppm nitrite as NO2- plus molybdate as MoO42- (where each of nitrite and molybdate is present in an amount of at least 600 ppm). Ready-to-use heavy-duty refrigerant/antifreeze products may contain (1) at least 1200 ppm nitrite as NO2- or (2) a minimum combined concentration of 780 ppm nitrite as NO2- plus molybdate as MoO42- (where each of nitrite and molybdate is present in an amount of at least 300 ppm).

[0072] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include molybdate ions. In some embodiments, the molybdate ions are derived from one or a plurality of molybdic acid salts (e.g., water-soluble molybdate salts). Representative salts of molybdic acid include, but are not limited to, alkali metal molybdate, alkaline earth metal molybdate, molybdenum trioxide, alkali metal heteropolymolybdates, and combinations thereof. Representative molybdates suitable for use as an optional additive in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, sodium molybdate, potassium molybdate, calcium molybdate, magnesium molybdate, lithium, sodium silicoeteropolymolybdate, sodium phosphoroeteropolymolybdate, and/or similar, and combinations thereof. Furthermore, alkali metal molybdate hydrates, alkaline earth metal molybdate and/or alkali metal heteropolymolybdates (e.g., sodium molybdate dihydrate) can also be used. In some embodiments, if molybdate ions are optionally present in a heat transfer fluid concentrate in accordance with the present teachings, the molybdate ions are not derived from lithium molybdate, calcium molybdate, strontium molybdate, magnesium molybdate and/or zinc molybdate. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings does not include lithium molybdate, calcium molybdate, strontium molybdate, magnesium molybdate and/or zinc molybdate. In some embodiments, the molybdate compound for use in the heat transfer fluid concentrate is sodium molybdate and/or sodium molybdate dihydrate.

[0073] The molybdate ion concentration may vary depending on the application. In some embodiments, one or more molybdate compounds present in the heat transfer fluid concentrate are soluble in the heat transfer fluid concentrate. In some embodiments, the molybdate compound is present in an amount of from about 0% by weight to about 10% by weight (i.e., up to about 10% by weight), in some embodiments about 0% by weight. weight to about 5% by weight (i.e., up to about 5% by weight), in some embodiments, about 0% by weight to 1% by weight (i.e., up to about 1% by weight) based on the total weight of the heat transfer fluid concentrate, and in some embodiments about 0.01 wt% to 0.6 wt% based on the total weight of the heat transfer fluid concentrate.

[0074] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include one or a plurality of azole compounds. Representative azole compounds that may be used in accordance with the present teachings include, but are not limited to, benzotriazole, tolyltriazole, methyl benzotriazole (e.g., 4-methyl benzotriazole, 5-methyl benzotriazole), butyl benzotriazole, other alkyl benzotriazoles (e.g., example, alkyl group containing from 2 to 20 carbon atoms), mercaptobenzothiazole, thiazole, imidazole, benzimidazole, indazole, tetrazole, tetrahydrotolyltyrazole, tetrahydrogenated benzotriazoles (for example, 4,5,6,7-tetrahydro-benzotriazole), 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, tetrahydrobenzotriazole, and/or similar, and combinations thereof. In some embodiments, the azole compound used in a heat transfer fluid concentrate in accordance with the present teachings includes a benzotriazole, a tolyltriazole, or a combination thereof.

[0075] Azole compounds used in accordance with the present teachings can be substituted or unsubstituted. Representative substituted azole compounds include, but are not limited to, substituted thiazoles, substituted imidazoles, substituted indazoles, substituted tatrazoles, and/or the like, and combinations thereof.

[0076] The concentration of the azole compound may vary depending on the application. In some embodiments, the amount of the azole compound varies from about 0.01% by weight to about 5% by weight based on the total weight of the heat transfer fluid concentrate. Within this range, the azole compound may be present in an amount greater than or equal to about 0.05% by weight and, in some embodiments, greater than or equal to about 0.1% by weight. Also within this range, the azole compound may be present in an amount of less than or equal to about 2% by weight and, in some embodiments, less than or equal to about 1% by weight.

[0077] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include corrosion inhibitors for copper and copper alloys. Representative copper and copper alloy corrosion inhibitors include, but are not limited to, compounds containing a 5- or 6-membered heterocyclic ring as the active functional group, wherein the heterocyclic ring contains at least one nitrogen atom (e.g., a azole compound of a type described above). In some embodiments, a copper and copper alloy corrosion inhibitor includes a substituted or unsubstituted compound - and/or a salt thereof (e.g., a sodium or potassium salt) - selected from the group consisting of benzotriazole, a hydrobenzotriazole (e.g., tetrahydrobenzotriazole), tolyltriazole, a hydrotolyltriazole (e.g., 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, and other tetrahydrobenzotriazoles as described in U.S. Patent No. 8,236,205 B1), methyl benzotriazole (e.g., e.g., 4-methyl benzotriazole, 5-methyl benzotriazole), alkyl benzotriazoles (e.g., benzotriazoles having a C2 to C20 alkyl group, including, but not limited to, butyl benzotriazole), mercaptobenzothiazole, thiazole, imidazole, benzimidazole, indazole, tetrazole , and/or similar, and combinations thereof. In some embodiments, one or more of the copper and copper alloy corrosion inhibitors mentioned above may be optionally substituted. In some embodiments, copper and copper alloy corrosion inhibitors may be present in the composition in an amount of from about 0.01% by weight to about 5% by weight. In some embodiments, the amount of the copper and copper alloy corrosion inhibitor varies from about 0.01% by weight to about 4% by weight based on the total weight of the heat transfer fluid concentrate. Within this range, the copper and copper alloy corrosion inhibitor may be present in an amount greater than or equal to about 0.05% by weight and, in some embodiments, greater than or equal to about 0.05% by weight. 1% by weight. Also within this range, the copper and copper alloy corrosion inhibitor may be present in an amount of less than or equal to about 2% by weight and, in some embodiments, less than or equal to about 1%. in weight.

[0078] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include a silicate. Silicates suitable for use in accordance with the teachings of the present invention include inorganic silicates and organic silicates. Useful inorganic silicates are represented by the general formula (2): (MO)mSiO(4-n/2)(OH)t (2); where M is a monovalent cation that forms a glycol or water-soluble silicate selected from the group consisting of sodium, potassium, lithium, rubidium and tetraorganoammonium cations; "m" has a value from 1 to 4 inclusive; "l" has a value from 0 to 3, inclusive; and "n" has a value from 1 to 4, inclusive, and is equal to the sum of "m" and "l".

[0079] The concentration of silicates present in the heat transfer fluid concentrate may vary depending on the application. In some embodiments, the silicate may be present in the heat transfer fluid concentrate in an amount of from about 0 ppm to about 8,000 ppm as Si (i.e., up to about 8,000 ppm), in some embodiments of from about 0 ppm to about 2000 ppm as Si (i.e., up to about 2000 ppm), in some embodiments from about 0 ppm to about 1000 ppm (i.e., up to about 1000 ppm ) as Si and in some embodiments less than about 700 ppm as Si in the heat transfer fluid concentrate.

[0080] Useful organic silicates include silicate esters represented by the general formula (3): Si(OR)4 (3); where R is selected from the group consisting of C1 to C36 alkyl, aryl, alkoxyalkyl, alkoxyaryl, hydroxyalkoxy and mixtures thereof. In some embodiments, a tetraalkylorthosilicate ester with alkyl groups containing 1 to 20 carbon atoms (e.g., tetramethylorthosilicate, tetraethylorthosilicate, and the like) can be used. The silicate ester is present in the heat transfer fluid concentrate formulation in an amount of from about 0% to about 5% by weight (i.e., up to about 5% by weight), e.g. about 0.01 to about 5% by weight, based on the total weight of the heat transfer fluid.

[0081] Colloidal silica can also be included for use as a corrosion inhibitor in accordance with the present teachings. Colloidal silica has a nominal particle size between about 1 nm and about 200 nm. In some embodiments, the particle size of the colloidal silica is about 1 nm to about 100 nm. In other embodiments, the diameter of the colloidal silica particle is between about 1 nm and about 40 nm. Suitable colloidal silicas for use in accordance with the teachings of the present invention include, but are not limited to, Ludox colloidal silica from DuPont or Grace Division, Nyacol and/or Bindzil colloidal silica from Akzo Nobel-Eka Chemicals, Snowtex colloidal silica from Nissan Chemical , as well as colloidal silica from Nalco and other suppliers. While not wishing to be limited to any particular theory nor intending to limit in any degree the scope of the appended claims and their equivalents, it is herein believed that by using colloidal silica in a heat transfer fluid, nanoparticles can increase heat transfer efficiency and /or heat capacity of heat transfer fluids. In some embodiments, colloidal silica is present in the formulation in an amount of from about 0 ppm to about 20,000 ppm (i.e., up to about 20,000 ppm) and, in some embodiments, from about 0 ppm to about of 2,000 ppm (i.e., up to about 2,000 ppm) of heat transfer fluid concentrate.

[0082] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may include a silicate stabilizer. Representative silicate stabilizers for use in accordance with the present teachings include, but are not limited to, a silicate stabilizing organosilane compound. As used herein, the term "organosilane" refers to a silane (i.e., a monomeric silicon chemical) that contains at least one carbon-silicon (Si-C) bond structure. Organosilane silicate stabilizing compounds for use in accordance with the present teachings include, but are not limited to, sodium 3-(trihydroxysilyl)-propylmethylphosphonate (CAS No. 84962-98-1 or silicone Q1-6083 from Dow Corning Corp. of Midland, MI); polyalkyleneoxidesaloxysilane [for example, methoxypolyethyleneoxypropyltrimethoxysilane having the formula: CH3O(CH2CH2O)mC3H6Si(OCH3)3, where m has an average value of 7.2 or methoxypolyethyleneoxypropyltripopoxysilane having the formula CH3O(CH2CH2O)7C3H6Si(OC3H7)3]; Silquest® Y-5560 or Silquest® Y-5630 from Momentive Performance Materials, Inc. (Waterford, NY); 3-(trihydroxysilyl)-propyl ethoxyl phosphonate sodium salts [e.g., (HO)3Si-C3H6-P(O)(ONa)(OC2H5)]; one or more of the alkali metal siliconate silylalkylphosphonates described in U.S. Patent No. 4,370,255; one or more of the arylalkyl silicone sulfates described in EP Patent No. 0061694B1; one or more of the silicate stabilizers described in U.S. Patent No. 4,629,602; one or more of the silicate stabilizers described in U.S. Patent Nos. 3,337,496 and 3,341,469; and/or similar; and combinations thereof.

[0083] The concentration of silicate stabilizer may vary depending on the application. In some embodiments, the amount of silicate stabilizer varies from about 0% by weight to about 5% by weight (i.e., up to about 5% by weight) based on the total weight of the fluid concentrate. heat transfer. In some embodiments, the amount of silicate stabilizer present in the heat transfer fluid concentrate is proportional to the amount of silicate present in the heat transfer fluid concentrate, where the ratio of silicate:silicate stabilizer varies from about from 20:1 to about 1:10 by weight. In some embodiments, the silicate:silicate stabilizer ratio varies from about 10:1 to about 1:2 by weight.

[0084] In some embodiments, the silicate component in the heat transfer fluid may be a copolymer of silicate and an organosilane. Examples include, but are not limited to, phosphonate-silicate, sulfonate-silicate, carboxylate-silicate and siloxane-silicate copolymers used in silicate-containing antifreeze/coolant compositions. These copolymers may be preformed or may be formed in situ by combining a water-soluble silicate and a water-soluble phosphonate silane, sulfonate silane, or carboxylate silane in an aqueous solution at room temperature. While not wishing to be bound by any particular theory nor intending to limit in any degree the scope of the appended claims or their equivalents, it is herein believed that such copolymers can provide improved metal corrosion inhibition over the use of simple alkali metal silicates once that organosilane-silicate copolymers substantially inhibit the gelation tendency of water-soluble silicate at a pH between about 7 and about 11 in glycol-water based antifreeze/coolant solutions. Representative silicate-organosilane copolymers that may be used in accordance with the present teachings include, but are not limited to, those described in U.S. Patent Nos. 3,198,820; 3,337,496; 3,341,496; 3,312,622; 3,248,329; 3,203,969; 4,093,641; 4,287,077; 4,333,843; 4,352,742; 4,354,002; 4,362,644; 4,434,065, 4,370,255; 4,629,602; 4,701,277; 4,772,408; and 4,965,344; European Patent No. 0,061,694 B1; and Patent Application Publication No. 2006/0017044A1.

[0085] Heat transfer fluid concentrates in accordance with the present teachings may include one or a plurality of water-soluble polymers (polyelectrolyte). Illustrative examples of water-soluble polymers suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include water-soluble polymers, such as polyelectrolyte dispersants derived from a polymerizable monomer. The polymerizable monomer contains at least one group selected from the group consisting of unsaturated carboxylic acids or salts, unsaturated amides, unsaturated acid anhydrides, unsaturated nitriles, unsaturated carbonyl halides, unsaturated carboxylate esters, unsaturated ethers, unsaturated alcohols, unsaturated sulfonic acids or salts , unsaturated phosphonic acids or salts, unsaturated phosphinic acids or salts, and/or similar, and combinations thereof.

[0086] In some embodiments, water-soluble polymers suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include homopolymers, copolymers, terpolymers and interpolymers having (1) at least one monomeric unit containing a monoacid - or monoethylenically unsaturated C3 to C16 dicarboxylic acid or its alkali metal or ammonium salts; or (2) at least one monomeric unit containing a monoethylenically unsaturated C3 to C16 mono- or dicarboxylic acid derivative such as an amide, nitrile, carboxylate ester, acid halide (e.g., acid chloride), acid anhydride, and/or similar, and combinations thereof. In some embodiments, a water-soluble polymer suitable for use in accordance with the present teachings may include at least 5% mer units of (1) or (2), and in some embodiments, at least 10% mer units ( 1 or 2).

[0087] Representative monocarboxylic acids suitable for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, acrylic acid, methacrylic acid, acid ethyl acrylic, vinylacetic acid, allylacetic acid and crotonic acid.

[0088] Representative monocarboxylic acid esters for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, butyl acrylate, butyl acrylate, n-hexyl, t-butylaminoethyl methacrylate, diethylaminoethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, methyl acrylate, methyl methacrylate, tertiary butylacrylate and vinyl acetate.

[0089] Representative dicarboxylic acids suitable for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, maleic acid, itaconic acid, fumaric acid, citaconic acid, mesaconic acid and methylenemalonic acid.

[0090] Representative amides suitable for use in producing water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, acrylamide (or 2-propenamide), methacrylamide, ethyl acrylamide, ethyl acrylamide, propyl acrylamide, N-t-butylacrylamide, tertiary butyl methacrylamide, tertiary octyl acrylamide, N,N-dimethylacrylamide (or N,N-dimethyl-2-propenamide), dimethylaminopropyl methacrylamide, cyclohexyl acrylamide, benzyl methacrylamide, vinyl acetamide, sulfomethylacrylamide, sulfoethylacrylamide, 2-hydroxy-3-sulfopropyl acrylamide, sulfophenylacrylamide, N-vinyl formamide, N-vinyl acetamide, 2-hydroxy-3-sulfopropyl acrylaide, N-vinyl pyrrolidone (a cyclic amide ), 2-vinylpyridine, 4-vinylpyridene and carboxymethylacrylamide.

[0091] Representative anhydrides suitable for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, maleic anhydride (or 2,5- furandione) and succinic anhydride.

[0092] Representative nitriles suitable for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, acrylonitrile and methacrylonitrile.

[0093] Representative acid halides suitable for use in the production of water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, acrylamidopropyltrimethylammonium chloride, diallyldimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.

[0094] In some embodiments, a water-soluble polymer for use in a heat transfer fluid concentrate with the present teachings contains at least one monomeric unit selected from the group consisting of allyl hydroxypropylsulfonate, AMPS, or 2-acrylamido-2 acid -methylpropane sulfonic acid, polyethylene glycol monomethacrylate, vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethyl propane sulfonic acid, metalyl sulfonic acid, allyloxybenzenesulfonic acid, 1,2-dihydroxy-3-butene, allyl alcohol, allyl phosphonic acid, ethylene glycoldiacrylate , aspartic acid, hydroxamic acid, 2-ethyl-oxazoline, adipic acid, diethylenetetramine, ethylene oxide, propylene oxide, ammonia, ethylene diamine, dimethylamine, diallyl phthalate, 3-allyloxy-2-hydroxy propane sulfonic acid, monomethacrylate polyethylene glycol, sodium styrene sulfonate, an alkoxylated allyl alcohol sulfonate, and/or the like, and combinations thereof.

[0095] In some embodiments, the water-soluble polymer suitable for use in a heat transfer fluid concentrate in accordance with the present teachings contains at least 5 mol% mer units (e.g., as polymerized units) resulting from polymerization of one or more monomers selected from the group consisting of (a) acrylic acid, methacrylic acid, crotonic acid, vinyl acetic acid, 4-methyl-4-penenoic acid, maleic acid, maleic anhydride, 1,2,3,6 anhydride - tetrahydrophthalic, 3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, bicyclo[2,2,2]-5-octene-2,3-dicarboxylic anhydride , 3-methyl-1,2,6-tetrahydrophthalic anhydride, 2-methyl-1,3,6-tetrahydrophthalic anhydride, itaconic acid, mesaconic acid, methylenemalonic acid, fumaric acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid , 3-allyloxy-2-hydroxypropane sulfonic acid, allyl phosphonic acid, allyloxybenzenesulfonic acid 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, allylsulfonic acid, other acrylamidomethyl propane sulfonic acids, metalyl sulfonic acid, isoprophenylsulfonic acid, vinylphosphonic acid , styrenesulfonic acid, vinylsulfonic acid, aspartic acid, hydroxamic acid, adipic acid and the alkali metal or ammonium salts of any of the above; (b) methyl acrylate, ethyl acrylate, butyl acrylate, n-hexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butylaminoethyl methacrylate, diethylaminoethyl acrylate, hydroxyethyl methacrylate , hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, tertiary butylacrylate, polyethylene glycol monomethacrylate, phosphoethyl methacrylate and vinyl acetate; (c) acrylamide (or 2-propenamide), methacrylamide, ethyl acrylamide, propyl acrylamide, N-t-butylacrylamide, tertiary butyl methacrylamide, octyl tertiary acrylamide, N-methylacrylamide, N,N-dimethylacrylamide (or N,N-dimethyl-2- propenamide), dimethylaminopropyl methacrylamide, cyclohexyl acrylamide, benzyl methacrylamide, vinyl acetamide, sulfomethylacrylamide, sulfoethylacrylamide, 2-hydroxy-3-sulfopropyl acrylamide, sulfophenylacrylamide, N-vinyl formamide, N-vinyl acetamide, 2-hydroxy-3-sulfopropyl acrylamide, N -vinyl pyrrolidone (a cyclic amide), 2-vinylpyridene, 4-vinylpyridene and carboxymethylacrylamide; (d) maleic anhydride (or 2,5-furandione) and succinic anhydride; acrylonitrile and mtacrylonitrile; (e) acrylamidopropyltrimethylammonium chloride, diallyldimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride; (f) 1,2-dihydroxy-3-butene, allyl alcohol, ethylene glycoldiacrylate, 2-ethyl-oxazoline, diethylenetriamine, ethylene oxide, propylene oxide, ammonia, styrene ethylene diamine, dimethylamine, diallyl phthalate, monomethacrylate of polyethylene glycol, sodium styrene sulfonate and an alkoxylated allyl alcohol sulfonate; and (b) combinations thereof.

[0096] In some embodiments, a representative allyl alkoxy alcohol sulfonate monomer for use in preparing a water-soluble polymer in accordance with the present teachings has the structure shown in general formula (4): where R1 is a hydroxyl-substituted alkyl or alkylene radical having 1 to about 10 carbon atoms or R1 is an unsubstituted alkyl or alkylene radical having 1 to 10 carbon atoms or R1 is -(CH2CH2-O)n-, - [CH2-CH(CH3)-O]n- or combinations thereof; where "n" is an integer from about 1 to about 50; where R2 is H or a (C1-C3)lower alkyl group; where anionic; and where n is 0 or 1. In some embodiments, a=1.

[0097] Representative water-soluble polyelectrolyte polymers suitable for use in a heat transfer fluid concentrate in accordance with the present teachings may, in some embodiments, have a molecular weight (MW) ranging from about 200 Daltons to about 200,000 Daltons. In other embodiments, suitable water-soluble polyelectrolyte polymer dispersants have a molecular weight (MW) ranging from about 500 Daltons to about 20,000 Daltons.

[0098] Illustrative water-soluble polyelectrolyte polymers suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, polycarboxylates. Representative polycarboxylates include, but are not limited to (1) polyacrylic or polyacrylate acids, acrylate-based polymers, copolymers, terpolymers and quad-polymers such as acrylate/acrylamide copolymers, acrylate/AMPS copolymers (acrylamide methylene sulfonic acid or 2 -acrylamido-2-methyl-1-propanesulfonic acid) or acrylamidoalkane sulfonic acid, acrylate/sulfonate copolymers, acrylate/hydroxyalkyl acrylate copolymers, acrylate/alkyl acrylate copolymers, acrylate/AMPS/alkyl acrylamide terpolymers, acrylate terpolymers /acrylamidoalkane sulfonic acid/styrene sulfonic acid (or water-soluble salts), acrylate/acrylamide/sulfoalkylacrylamide terpolymers, acrylic acid/allyloxy-2-hydroxypropylsulfonic acid (AHPSE) terpolymer/polyethylene glycol allyl ether, acrylate/methacrylate methyl ester /2-propane-1-sulfonic acid, 2-methyl quad-polymers, sodium salt/benzenesulfonic acid, 4-[(2-methyl-2-propenyl)oxy], sodium salt; (2) polymethacrylic acids or polymethacrylate, methacrylate-based polymers, copolymers, terpolymers and quad-polymers, wherein a monomer of the corresponding acrylate-based polymers listed in (1) is replaced by methacrylate or methacrylic acid; (3) polymaleic acid or maleic anhydride polymers, maleic acid-based polymers, their copolymers, terpolymers and quad-polymers, wherein a monomer of the corresponding acrylate-based polymers listed in (1) is replaced by maleic acid or maleic anhydride ; (4) polyacrylamides, modified acrylamide-based polymers and acrylamide-based copolymers, terpolymers and quad-polymers, wherein a monomer of the corresponding acrylate-based polymers listed in (1) is replaced by acrylamide; (5) copolymers, terpolymers and quad-polymers based on sulfonic acid or its water-soluble salts; copolymers, terpolymers and quad-polymers based on phosphonic acid and quad-polymers or their water-soluble salts; copolymers, terpolymers and quad-polymers based on phosphinic acid or its water-soluble salts; (6) vinylpyrrolidone-based homopolymers and copolymers; (7) alkylene oxide-based copolymers and terpolymers; and combinations comprising one or more of the above.

[0099] A water-soluble polymer for use in a heat transfer fluid concentrate in accordance with the present teachings may also be either a polyether polyamino methylene phosphonate as described in U.S. Patent No. 5,338,477 or a phosphine acid polyacrylate.

[0100] Representative examples of commercially available polymers suitable for use as water-soluble polyelectrolyte polymers in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, (a) the Good series of polymers -Rite® K-700 shown in Table 1 available from Noveon (or Lubrizol), (b) the polymers shown in Table 2 available from AkzoNobel, and (c) the polymers shown in Table 3 available from Dow (Rohm & Haas).

[0101] Polymers supplied by Noveon (or Lubrizol) that can be used as a water-soluble polyelectrolyte polymer in the heat transfer fluid concentrate include those shown in Table 1 below. Table 1. Polymers Supplied by Noveon (or Lubrizol): Good-Rite® K-700 Series Polymers PAA = Polyacrylate, NaPAA = Sodium Polyacrylate, NaPMAA = Sodium Polymethacrylate, AA = Acrylic Acid, AS = Sulfonic Acid or AMPS, SS = Sodium Styrene Sulfonate 'Active Solids' = 'Total Solids' - 'Counterions (sodium) of post-polymerization neutralization with NaOH *pH of a 1% solution **Includes moisture content NP Unpublished

[0102] Polymers supplied by AkzoNobel that can be used as a water-soluble polyelectrolyte polymer in the heat transfer fluid concentrate include those shown in Table 2 below. Table 2. Typical Property of AkzoNobel Aquatreat Industrial Water Treatment Products

[0103] AR-335 is polyacrylamide; AR-545 and AR-546 are AA/AMPS copolymers; Aquatreat AR-540 is a terpolymer of Acrylic acid (AA)/2-propenoic acid, 2-methyl, methyl ester/benzenesulfonic acid, 4-[(2-methyl-2-propenyl)oxy]-, sodium salt/ 2-propene-1-sulfonic acid, 2-methyl, sodium salt. Versa TL-4 = styrene/sulfonated maleic anhydride copolymer. Versa Tl-3 is the dry form of Versa TL-4. AR-978 is acrylic acid/maleic acid copolymer; AR-980 is an Acrylic Acid/Maleic Acid/Nonionic Acid Monomer Terpolymer.

[0104] Polymers provided by Dow (Rohm & Haas) that can be used as a water-soluble polyelectrolyte polymer in the heat transfer fluid concentrate include those shown in Table 3 below. Table 3. Polymers available from Dow (Rohm & Haas)

[0105] Note: Acumer 2000 and 2100 are carboxylic acid/sulfonic acid copolymers (i.e., AA/AMPS copolymers); Acumer 3100 and Acumer 5000 are acrylic acid/t-butyl acrylamide/2-acrylamido-2-methyl propane sulfonic acid terpolymers. Optidose 1000, 2000 and Optidose 3100 are labeled versions of Acumer 1000, 2000 and 3100 respectively.

[0106] In some embodiments, a water-soluble polymer suitable for use in a heat transfer fluid concentrate in accordance with the present teachings is selected from commercially available polymers: (1) polymers available from BASF under the brands SOKALAN and TAMOL , including, but not limited to, Sokalan CP 9 (maleic acid-based polymer), Sokalan CP 10, CP 42, 10S, 12S (all are acrylate-based polymers), 13S, Sokalan HP 22 G, HP 25, HP 59 and HP165 (polyvinylpyrrolidone), Sokalan PA 15, PA 20, PA 25 Cl, PA 30 Cl, PA 40, Sokalan PM 10 I, PM 70, Tamol VS and other similar products; (2) polymers available from Cytec under the CYANAMER brand including, but not limited to, P-35, P-70, P-80, A-100L and A-15 (all are acrylate or acrylamide based polymers or copolymers) It's similar; (3) polymers available from Biolab additives under the brand names BLECLENE and BELSPERSE including, but not limited to, Beclene 200 (maleic acid homopolymer), 283 (maleic acid terpolymer), 400 (sulfonated polycarboxylic phosphine acid), and 499 (phosphono acid sulfonated polycarboxylic acid); and Belspere 161 (polycarboxylic phosphine acid) and 164 (polycarboxylic phosphine acid) and the like and (4) water-soluble polymer products available from Nalco (e.g., acrylic acid/2-acrylamido-2-methylpropyl sulfonic acid copolymers, polyether polyamine phosphonate as described in U.S. Patent No. 5,338,477 and acrylic acid/acrylamide/acrylamidomethanesulfonic acid terpolymers), GE Betz (e.g., acrylic acid/polyethylene glycol allyl ether copolymers, acrylic acid/allyloxy acid-2- hydroxypropyl sulfonic acid (or AHPSE)/polyethylene glycol allyl ether and acrylic acid/AHPSE copolymers), Chemtreat [e.g., allyloxybenzenesulfonic acid quad-polymers (~3.5 mol %)/metalyl sulfonic acid (~2.5 mol %) mol)/methyl methacrylate (1318 mol%)/acrylic acid (76-81 mol%)], Ciba, SNF Floeger, Rhone-Poulenc, Stockhausen, Hercules, Henkel, Allied Colloids, Hoechst Celanese, Ashland Chemical Company, Kurita Water Industries, Ltd., Nippon Shokubai Co. and other suppliers.

[0107] Additional water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, those described in U.S. patents: 3,085,916; 3,578,589; 3,709,815; 3,806,367; 4,499,002; 4,510,059; 4,532,048; 4,563,284; 4,566,973; 4,566,974; 4,640,793; 4,707,271; 4,762,621; 4,784,774; 4,885,097; 4,952,326; 4,952,327; 5,023,001; 5,658,465; 6,361,768B1; 4,556,493; 4,581,145; 4,457,847; 4,703,092; 4,801,388; 4,919,821; 4,929,425; 5,035,806; 5,049,310; 5,080,801; 5,128,419; 5,167,828; 5,171,459; 5,213,691; 5,216,086; 5,260,386; 5,422,408; 5,403,493; 5,534,611; 5,726,267; 5,736,405; 5,776,875; 5,750,070; 5,788,866; 5,858,244; 5,876,623; 6,005,040; 6,017,994; 6,022,401; 6,153,106; 6,225,430B1; 6,232,419B1; 6,312,644B1; 6,344,531B1; 6,380,431B1; 6,426,383B1; 6,440,327B1; 6,461,518B1; 6,645,428B1; 7,115,254B1; 4,443,340; 4,659,480; 4,659,482; 4,913,822; 4,929,362; 4,929,695; 4,931,206; 4,944,885; 5,030,748; 5,078,891; 5,100,558; 5,102,555; 5,108,619; 5,128,427; 5,139,643; 5,147,555; 5,158,622; 5,158,685; 5,169,537; 5,180,498; 5,194,620; 5,211,845; 5,234,604; 5,248,438; 5,242,599; 5,256,302; 5,264,155; 5,271,847; 5,271,862; 5,282,905; 5,320,757; 5,332,505; 5,342,540; 5,350,536; 5,374,336; 5,378,327; 5,378,372; 5,393,456; 5,445,758; 5,512,183; 5,518,630; 5,527,468; 5,575,920; 5,601,754; 6,228,950B1; 6,444,747B1; 6,641,754B2; 4,517,098; 4,530,766; 4,711,725; 5,055,540; 5,071,895; 5,185,412; 5,223,592; 5,277,823; 5,342,787; 5,395,905; 5,401,807; 5,420,211; 5,451,644; 5,457,176; 5,516,432; 5,531,934; 5,552,514; 5,554,721; 5,556,938; 5,597,509; 5,601,723; 5,658,464; 5,755,972; 5,866,664; 5,929,098; 6,114,294; 6,197,522B1; 6,207,780B1; 6,218,491B1; 6,251,680B1; 6,335,404B1; 6,395,185; 5,023,368; 5,547,612; 5,650,473; 5,654,198; 5,698,512; 5,789,511; 5,866,012; 5,886,076; 5,925,610; 6,040,406; 6,995,120B2; 7,087,189B2; 5,346,626; 5,624,995; 5,635,575; 5,716,529; 5,948,268; 6,001,264; 6,162,391; 6,368,552B1; 6,656,365B2; 6,645,384B1; 5,000,856; 5,078,879; 5,087,376; 5,124,046; 5,153,390; 5,262,061; 5,322,636; 5,338,477; 5,378,368; 5,391,303; 5,407,583; 5,454,954; 5,534,157; 5,707,529; 6,691,715B2; 6,869,998B2; 4,372,870; 5,124,047; 4,797,224; 4,485,223; 5,254,286; 4,460,477; 5,015,390; 4,933,090; 4,868,263; 4,895,664; 4,895,916; 5,000,856; 4,900,451; 4,584,105; 4,872,995; 4,711,726; 4,851,490; 4,849,129; 4,589,985; 4,847,410; 4,657,679; 4,801,387; 4,889,637; 4,604,211; 4,710,303; 4,589,985; 4,324,664; 3,752,760; 4,740,314; 4,647,381; 4,836,933; 4,814,406; 4,326,980; 4,008,164; 5,246,332; and 5,187,238. Additional water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, those described in the following European patents: EP 0,297,049B1; EP 0360746B1; and EP 0,879,794B1. Additional water-soluble polymers that can be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, those described in the following U.S. patent application publications: 2006/0191852A1; 2005/0202995A1; 2002/0195583A1; 2004/00225093A1; 2005/0009959A1; and 2005/0092211A1.

[0108] In some embodiments, the water-soluble polymer used in a heat transfer fluid concentrate in accordance with the present teachings includes an acrylate-based polymer. Representative acrylate-based polymers suitable for use in accordance with the present teachings include, but are not limited to, acrylate-based homopolymer, acrylate-based copolymer, acrylate-based terpolymer, acrylate-based quad-polymer, and combinations. of the same. In some embodiments, the acrylate-based polymer comprises polyacrylate.

[0109] For some of the embodiments in which a heat transfer fluid concentrate in accordance with the present teachings further includes magnesium ions and the water-soluble polymer includes an acrylate-based polymer, the polymer stabilizer concentration ratio active acrylate-based magnesium ion concentration is between about 1 and about 25 and, in other embodiments, is optionally greater than about 5 and less than about 25. For some of the embodiments in which a concentrate of heat transfer fluid in accordance with the present teachings further includes calcium ions and the water-soluble polymer includes an acrylate-based polymer, the ratio of acrylate-based polymer concentration to calcium ion concentration in the heat transfer fluid concentrate heat transfer fluid is greater than 4 and less than about 110. In some embodiments, the ratio of acrylate-based polymer concentration to calcium ion concentration in the heat transfer fluid concentrates is greater than about 7 and less than about 80.

[0110] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may optionally further include one or a plurality of phosphonocarboxylates. Phosphonocarboxylates are phosphonated compounds having the general formula (5) H[CHRCHR]n-PO3M2 (5) where at least one R group in each unit is COOM, CH2OH, sulfone or phosphono group and the other R group - which can be the same or other than the first group R - is a hydrogen or a COOM group, hydroxyl, phosphono, sulfone, sulfate, C1-7 alkyl, C1-7 alkenyl or a C1-7 alkyl or C1-7 alkenyl group substituted by carboxylate, phosphono, sulfone , sulfate and/or hydroxyl; where n is 1 or an integer greater than 1; and where each M is hydrogen or an alkali metal ion such as a sodium ion, potassium ion and the like. Furthermore, at least one COOM group will be present in one of the R groups. In some embodiments, the phosphonocarboxylates are phosphonated oligomers or mixture of phosphonated oligomers of maleic acid of formula (6) H[CH(COOM)CH(COOM)]n- PO3M2 (6) where n is 1 or an integer greater than 1 and M is a cationic species (e.g., alkali metal cations) so that the compound is soluble in water. Representative phosphonocarboxylates include, but are not limited to, phosphonosuccinic acid, 1-phosphono-1,2,3,4-tetracarboxybutane and 1-phosphono-1,2,3,4,5,6-hexacarboxyexane. Phosphonocarboxylates can be a mixture of compounds having formula (6) with different values for "n". The average value of "n" may be 1 to 2 or, in some embodiments, 1.3 to 1.5. The synthesis of phosphonocarboxylates is known and described in U.S. Patent No. 5,606,105. Phosphonocarboxylates are separate and different from the carboxylates described above.

[0111] In a heat transfer fluid concentrate in accordance with the present teachings, a phosphonocarboxylate may optionally be present in an amount ranging from about 10 ppm to about 500 ppm based on the total weight of the heat transfer fluid concentrate. heat transfer fluid. Within this range, the phosphonocarboxylates may be present in an amount greater than or equal to about 20 ppm and, in some embodiments, greater than or equal to about 40 ppm. Also within this range, the phosphonocarboxylate may be present in an amount less than or equal to about 40 ppm and, in some embodiments, less than or equal to about 300 ppm. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings is free of any phosphonocarboxylate.

[0112] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings may further include one or a plurality of phosphinocarboxylates. Phosphinocarboxylates are compounds having the general formula (7) H[CHR1CHR1]n-P(O2M)-[CHR2CHR2]mH (7) where at least one R1 group in each unit is a COOM, CH2OH, sulfone or phosphono group and the other R1 group - which may be the same or different from the first group R1 - is a hydrogen or a COOM group, hydroxyl, phosphono, sulfone, sulfate, C1-7 alkyl, C1-7 alkenyl or a substituted C1-7 alkyl or C1-7 alkenyl group with carboxylate, phosphone, sulfone, sulfo, sulfate and/or hydroxyl; where n is an integer equal to or greater than 1; and where each M is hydrogen or an alkali metal ion such as a sodium ion, potassium ion and the like. Similarly, at least one R2 group in each unit is a COOM, CH2OH, sulfone or phosphono group and the other R2 group - which may be the same or different from the first R2 group - is hydrogen or a COOM, hydroxyl, phosphono, sulfono group, sulfate, C1-7 alkyl, C1-7 alkenyl or a C1-7 alkyl or C1-7 alkenyl group substituted with carboxylate, phosphone, sulfone, sulfate and/or hydroxyl; and where m is an integer equal to or greater than 0. Furthermore, at least one COOM group will be present in one of the groups R1 and R2. Representative phosphinocarboxylates include, but are not limited to, phosphinosuccinic acid and water-soluble salts thereof, phosphinicbis(succinic) acid and water-soluble salts thereof, and phosphinosuccinic acid oligomer and salts thereof as described in U.S. Patent Nos. 6,572,789 and 5,018,577. Phosphonocarboxylates can be a mixture of compounds having formula (6) with different values for "n" and "m". Phosphinocarboxylates are separate and different from the carboxylates described above.

[0113] In a heat transfer fluid concentrate in accordance with the present teachings, a phosphinocarboxylate may optionally be present in an amount ranging from about 10 ppm to about 500 ppm based on the total weight of the heat transfer fluid concentrate. heat transfer fluid. Within this range, the phosphinocarboxylate may be present in an amount greater than or equal to about 20 ppm and, in some embodiments, greater than or equal to 40 ppm. Also within this range, the phosphinocarboxylate may be present in an amount less than or equal to about 400 ppm and, in some embodiments, less than or equal to about 300 ppm. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings is free of any phosphinocarboxylate.

[0114] In some embodiments, heat transfer fluid concentrate in accordance with the present teachings may further optionally include one or more additional components. The total combined concentration of optional additional components can range from about 0.0% by weight to about 15% by weight (i.e., up to about 15% by weight) based on the total weight of the fluid concentrate. of heat transfer. In some embodiments, the total combined concentration of the optional additional components is between about 0.0001% by weight and about 10% by weight based on the total weight of the heat transfer fluid concentrate. In other embodiments, the total combined concentration of the optional additional components is between about 0.001% by weight and about 5% by weight based on the total weight of the heat transfer fluid concentrate. In further embodiments, the total combined concentration of the optional additional components is between about 0.01% by weight and about 3% by weight based on the total weight of the heat transfer fluid concentrate.

[0115] Representative additional components that may optionally be present in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, colorants, antifoaming or defoaming agents, pH adjusting agents, phosphonates (e.g. , AMP or aminotrimethylene phosphonic acid; HEDP or 1-hydroxy ethylidene-1,1-diphosphonic acid; HPA or hydroxyphosphono-acetic acid or 2-hydroxy phosphono acetic acid; PBTC or 2-butane phosphono-1,2,4-tricarboxylic acid ; PCAM or phosphono acid carboxylate mixture; and/or Bricorr 288, which is a mixture of sodium salts of organophosphonic acid H- [CH(COONa)CH(COONa)]n-PO3Na2, where n <5 and naverage = 1 ,4 and other phosphonates), phosphinate (e.g. PSO or phosphinic acid oligomers, which is a mixture of mono-, bis- and oligomeric phosphinic acid adduct, and other phosphinate), biocides, polymer dispersants, deposition inhibitors particles, surfactants, bittering agents, additional corrosion inhibitors, other refrigerant/antifreeze additives, and/or similar, and combinations thereof. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings may specifically exclude one or more of these optional additional components (e.g., be substantially "free" of one or more of the additional components mentioned above).

[0116] Additional corrosion inhibitors that may optionally be included in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, salts of cyclohexenoic carboxylate compounds derived from tallow oil fatty acids ( for example, alkali metal salts, ammonium salts and/or the like) as well as amine compounds. Representative amine compounds include, but are not limited to, ethanolamine, diethanolamine, triethanolamine, morpholino, benzylamine, cyclohexylamine, dicyclohexilaine, hexylamine, AMP (2-amino-2-methyl-1-propanol or isobutanolamine), DEAE (diethylethanolamine), DEHA (diethyl hydroxylamine), DMAE (2-dimethylaminoethanol), DMAP (dimethylamino-2-propanol), MOPA (3-methoxypropylamine), and/or similar, and combinations thereof.

[0117] Representative dyes or pigments suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, "Uranine Yellow", "Uranine Dye", "Alizarine Green", "Chromatint Orange 1735" or "Green AGS liquid" by Abbeys Color Inc., or Chromatech Incorporated, "Chromatint Yellow 0963 Liquid Dye", "Chromatint Yellow 2741 Liquid Dye", "Chromatint Green 1572 dye", "Chromatint Green 2384 Dye", " Chromatint Violet 1579 Dye" by Chromatech Incorporated", "Acid Red#52" or Sulforhodamine B by Tokyo Chemical Industriy Co. or TCI America. "Orange II (Acid Orange 7)" or "Intracid Rhodamine WT (Acid Red 388) by Sensient Technologies or other suppliers.

[0118] Any suitable antifoam or defoaming agent, including, but not limited to, conventionally known type agents, can be used in heat transfer fluids in accordance with the present teachings. Representative defoamers that may be used in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, a polyalkylene glycol containing organo-modified polydimethylsiloxane, polyalkylene oxide siloxane copolymer, polyalkylene oxide, " PM-5150" available from Prestone Products Corp., "Pluronic L-61" and "Plurafac® LF 224 from BASF Corp., "Patcote 392", "Patcote 415" and other Patcote brand defoamers available from Hydrite Chemical Co. and other suppliers and "Foam Ban 136B" and other Foam Ban defoamers available from Munzing Chemie GmbH or affiliated companies. Optional defoamers may also include polydimethylsiloxane emulsion-based defoamers, including, but not limited to, PC-5450NF from Performance Chemicals , LLC in Boscawen NH; and CNC XD-55 and silicone base (e.g., SAG-10, Silbreak® 320) from OSI Specialties, Inc., Momentive Performance Materials Inc. in Waterford, NY, Dow Corning, and other suppliers; an ethylene oxide-propylene oxide (EO-PO) block copolymer and a propylene oxide-ethylene oxide-propylene oxide (PO-EO-PO) block copolymer (e.g., Pluronic L61, Pluronic L81 and other Pluronic and Pluronic C products); poly(ethylene) oxide or poly(propylene) oxide, for example PPG 2000 (e.g. polypropylene oxide with an average molecular weight of 2000 Daltons); polydiorganosiloxane-based products (for example, products containing polydimethylsiloxane (PDMS) and the like); fatty acids or fatty acid esters (e.g. stearic acid and the like); a fatty alcohol, an alkoxylated alcohol and a polyglycol; a polyether polyol acetate, a polyether ethoxylated sorbitol hexaoleate, and a poly(ethylene-propylene oxide)monoallyl ether oxide acetate; a wax, a naphtha, kerosene and an aromatic oil; and/or similar; and combinations thereof.

[0119] Representative biocides suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, various non-oxidizing biocides, such as glutaraldehyde, isothiazoline, 5-chloro-2-methyl- 4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2,2-dibromo-3-nitrilopropionamide, 2-bromo-2-nitropropane-1, 3-diol, methylene bis(thiocyanate), terbuthylazine, tetracis(hydroxymethyl)phosphonium sulfate, and/or similar, and combinations thereof.

[0120] Representative pH adjusting agents suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, alkali metal or alkaline earth metal hydroxides or oxides (e.g., sodium hydroxide). sodium, potassium hydroxide), inorganic phosphates (for example, sodium phosphate, potassium phosphate, sodium pyrophosphate and potassium pyrophosphate), and/or similar, and combinations thereof.

[0121] Representative nonionic surfactants suitable for use in a heat transfer fluid concentrate in accordance with the present teachings include, but are not limited to, fatty acid esters, such as sorbitan fatty acid esters, polyalkylene glycols, polyalkylene glycol esters, copolymers of ethylene oxide (EO) and propylene oxide (PO), polyoxyalkylene derivatives of a sorbitan fatty acid ester, and/or the like, and combinations thereof. In some embodiments, the average molecular weight of the nonionic surfactants is between about 55 and about 300,000, and in some embodiments, between about 110 and about 10,000. Representative sorbitan fatty acid esters include, but are not limited to, sorbitan monolaurate (e.g., sold under the trade name Span®, Arlacel® 20, S-MAZ® 20Ml), sorbitan monopalmitate (e.g., Span® 40 or Arlacel® 40), sorbitan monostearate (e.g. Span® 60, Arlacel® 60 or S-MAZ® 60K), sorbitan monooleate (e.g. Span® 80 or Arlacel® 80), sorbitan monosesquioleate (e.g. Span® 83 or Arlacel® 83), sorbitan trioleate (e.g. Span® 85 or Arlacel® 85), sorbitan triesterate (e.g. S-MAZ® 65K) and sorbitan monothalate (e.g. S-MAZ® 90). Representative polyalkylene glycols include, but are not limited to, polyethylene glycols, polypropylene glycols and combinations thereof. Representative polyethylene glycols include, but are not limited to, CARBOWAX™ polyethylene glycols and methoxypolyethylene glycols from Dow Chemical Company (e.g., CARBOWAX PEG 200, 300, 400, 600, 900, 1000, 1450, 3350, 4000 & 8000, etc.) or PLURACOL® polyethylene glycols from BASF Corp. (e.g. Pluracol® E 200, 300, 400, 600, 1000, 2000, 3350, 4000, 6000 and 8000 etc). Representative polyalkylene glycol esters include, but are not limited to, mono- and di-esters of various fatty acids, such as MAPEG® polyethylene glycol esters from BASF (e.g., MAPEG® 200ML or PEG 200 Monolaurate, MAPEG® 400 DO or PEG 400 Dioleate, MAPEG® 400 MO or PEG 400 Monooleate and MAPEG® 600 DO or PEG 600 Dioleate, etc.). Representative copolymers of ethylene oxide (EO) and propylene oxide (PO) include, but are not limited to, various BASF Pluronic and Pluronic R block copolymer surfactants, DOWFAX nonionic surfactants, UCON™ fluids and DOW SYNALOX lubricants Chemical. Representative polyoxyalkylene derivatives of a sorbitan fatty acid ester include, but are not limited to, polyoxyethylene 20 sorbitan monolaurate (e.g., products sold under the trademarks TWEEN 20 or T-MAS 20), polyoxyethylene 4 sorbitan monolaurate ( e.g. TWEEN 21) polyoxyethylene 20 sorbitan monopalmitate (e.g. TWEEN 40), polyoxyethylene 20 sorbitan monostearate (e.g. TWEEN 60 or T-MAS 60K), polyoxyethylene 20 sorbitan monooleate (e.g. TWEEN 80 or T-MAS 80), polyoxyethylene 20 triestearate (e.g. TWEEN 65 or T-MAS 65K), polyoxyethylene 5 sorbitan monooleate (e.g. TWEEN 81 or T-MAS 81), polyoxyethylene 20 sorbitan trioleate ( for example, TWEEN 85 or T-MAS 85K), and/or similar, and combinations thereof.

[0122] In some embodiments, heat transfer fluid concentrates in accordance with the present teachings can be used in cooling systems and can provide corrosion inhibition properties. In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings contains (a) a freezing point depressant, water, or a combination thereof, where the freezing point depressant is present in an amount varying from about 1% by weight to about 99% by weight, based on a total weight of the heat transfer fluid concentrate; (b) an organophosphate, wherein the organophosphate is present in an amount ranging from about 0.002% by weight to about 5% by weight based on the total weight of the heat transfer fluid concentrate; (c) a carboxylic acid or salt thereof, wherein the carboxylic acid or salt thereof is present in an amount ranging from about 1% by weight to about 10% by weight based on the total weight of the concentrate of heat transfer fluid, wherein the carboxylic acid includes one or a plurality of C6 to C20 carboxylic acids, and where the one or plurality of C6 to C20 carboxylic acids is individually selected from the group consisting of an aliphatic monocarboxylic acid, an acid aliphatic dicarboxylic acid, an aromatic monocarboxylic acid, an aromatic dicarboxylic acid and combinations thereof; (d) calcium ion at a concentration of up to about 200 mg/L based on a total weight of the heat transfer fluid concentrate; (e) magnesium ion at a concentration of up to about 150 mg/L based on a total weight of the heat transfer fluid concentrate; (f) an azole compound present in an amount ranging from about 0.01% by weight to about 3% by weight based on the total weight of the heat transfer fluid concentrate; and (g) optionally, an additional component selected from the group consisting of an inorganic phosphate, lithium ion, zinc ion, nitrate ion, nitrite ion, molybdate ion, a phosphonate, a phosphinate, an acrylate-based polymer , a dye, a biocide, an antifoam, a surfactant, a dispersant, an anti-particle deposition agent, a wetting agent and combinations thereof. In some embodiments, the heat transfer fluid concentrate contains calcium ions at a concentration ranging from about 0.001 mg/L to about 200 mg/L based on a total weight of the heat transfer fluid concentrate. of heat and/or contains magnesium ions in a concentration ranging from about 0.001 mg/mL to about 150 mg/mL based on a total weight of the heat transfer fluid concentrate.

[0123] In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings is a homogeneous, single-phase solution at room temperature. In some embodiments, the heat transfer fluid concentrate in accordance with the present teachings is stable in storage at a temperature between about -10° C. and +100° C. In some embodiments, a heat transfer fluid concentrate and/or a ready-to-use heat transfer fluid derived therefrom (e.g., through dilution) will satisfy the properties and performance requirements of ASTM D3306.

[0124] In some embodiments, a heat transfer fluid concentrate in accordance with the present teachings can be diluted (e.g., with water) to form a heat transfer fluid. For example, in some embodiments, the heat transfer fluid concentrate may be diluted to about 10 vol%. at about 75% vol. to form a heat transfer fluid. In some embodiments, the water used for dilution is deionized water as described in Section 4.5 of ASTM D3306-10.

[0125] In some embodiments, the heat transfer fluid concentrate in accordance with the present teachings may be provided as a commercially available product. In other embodiments, a ready-to-use heat transfer fluid in which the heat transfer fluid concentrate has been pre-diluted to around 50 vol%. with water can be provided as a commercially available product. In preparing a ready-to-use heat transfer fluid through dilution, the optimum level of water added to the heat transfer concentrate under conditions of use can be determined by the requirements for protection against freezing, boiling and corrosion.

[0126] Heat transfer fluid concentrate that has not been diluted by the addition of water is not typically used in an engine cooling system as a heat transfer fluid due to its relatively low heat transfer coefficient (or specific heat ), high viscosity and high freezing point. In this way, heat transfer fluid concentrates can be diluted (e.g., to 30 vol. % to 60 vol. % solutions) by adding water before being used in engine cooling systems as cooling fluids. heat transfer. Vehicle manufacturers typically use 50% vol. of heat transfer concentrate diluted by water as factory fill fluid in vehicle cooling systems. Heat transfer fluid products that are pre-diluted by water to contain about 30% vol. to about 60% by vol. Heat transfer fluid concentrates are ready-to-use coolants because no more water is needed when they are added to a vehicle cooling system.

[0127] In a ready-to-use heat transfer fluid, the freezing point depressant may be present in an amount of from about 1% by weight to less than about 90% by weight based on the total weight of the fluid ready-to-use heat transfer system. Within this range, the amount of freezing point depressant may be greater than or equal to about 25% by weight, greater than or equal to about 30% by weight, greater than or equal to about 40% by weight, greater than or equal to about 50% by weight, greater than or equal to about 60% by weight, greater than or equal to about 70% by weight, greater than or equal to about 75% by weight, greater than or equal to about 80% by weight, greater than or equal to about 85% by weight, greater than or equal to about 86%, greater than or equal to about 87% by weight, greater than or equal to about 88% by weight, or greater than or equal to about 89% by weight, but less than about 90% by weight based on the total weight of the transfer fluid of heat ready to use. Also, within this range, the amount of the freezing point depressant may be less than or equal to about 30% by weight, less than or equal to about 40% by weight, less than or equal to about 50% by weight, less than or equal to about 55% by weight, less than or equal to about 60% by weight, less than or equal to about 70% by weight, less than or equal to about 75% by weight, less than or equal to about 80% by weight, less than or equal to about 85% by weight, less than or equal to about 86% by weight, less than or equal to about 87% by weight, less than or equal to about 88% by weight, or less than or equal to about 89% by weight, but not more than about 1% by weight based on weight total heat transfer fluid ready for use.

[0128] In the ready-to-use heat transfer fluid, organophosphate may be present in an amount of about 0.001% by weight to about 5% by weight, based on the total weight of the ready-to-use heat transfer fluid. . Within this range, the amount may be greater than or equal to about 0.005% by weight or, in some embodiments, greater than or equal to about 0.01% by weight. Also within this range, the amount may be less than or equal to about 3% by weight or, in some embodiments, less than or equal to about 1% by weight.

[0129] In the ready-to-use heat transfer fluid, the carboxylate may be present in an amount of about 0.5% by weight to about 8% by weight, based on the total weight of the ready-made heat transfer fluid. For use. Within this range, the amount may be greater than or equal to about 0.6% by weight or, in some embodiments, greater than or equal to about 0.7% by weight. Also within this range, the amount may be less than or equal to about 7% by weight or, in some embodiments, less than or equal to about 6% by weight.

[0130] For embodiments in which the ready-to-use heat transfer fluid includes one or more alkaline earth metal ions, the total amount of alkaline earth metal ion can vary from about 0.0001% by weight to about 0.02% by weight based on the total weight of the ready-to-use heat transfer fluid. Within this range, the amount may be greater than or equal to about 0.001% by weight or, in some embodiments, greater than or equal to about 0.002% by weight. Also within this range, the amount may be less than or equal to about 0.01% by weight or, in some embodiments, less than or equal to about 0.006% by weight.

[0131] For embodiments in which the ready-to-use heat transfer fluid includes calcium ion, the total amount of calcium ion may be greater than about 0.5 ppm based on the total weight of the heat transfer fluid ready to use. Within this range, the amount of calcium ion can be less than about 50 ppm. Also within this range, the amount of calcium ion may be less than or equal to about 20 ppm.

[0132] For embodiments in which the ready-to-use heat transfer fluid includes magnesium ion, the total amount of magnesium ion may be greater than about 0.5 ppm based on the total weight of the heat transfer fluid ready to use. Within this range, the amount of magnesium ion can be less than about 60 ppm. Also within this range, the amount of magnesium ion can be less than or equal to about 25 ppm.

[0133] For embodiments in which the ready-to-use heat transfer fluid includes strontium ion, the total amount of strontium ion may be greater than about 0.1 ppm based on the total weight of the heat transfer fluid ready to use. Within this range, the amount of strontium ion can be less than about 40 ppm. Also within this range, the amount of strontium ion can be less than or equal to about 20 ppm.

[0134] For embodiments in which the ready-to-use heat transfer fluid includes water-soluble inorganic phosphate, the total amount of water-soluble inorganic phosphate may be greater than about 0.5 ppm as P based on total weight of ready-to-use heat transfer fluid. Within this range, the amount of water-soluble inorganic phosphate may be less than or equal to about 2000 ppm as P. Also within this range, the amount of water-soluble inorganic phosphate may be less than or equal to about 500 ppm as P.

[0135] For embodiments in which the ready-to-use heat transfer fluid includes lithium ion, the total amount of lithium ion may be greater than about 0.001 ppm based on the total weight of the ready-to-use heat transfer fluid. use. Within this range, the amount of lithium ion can be less than about 6000 ppm. Also within this range, the amount of lithium ion may be less than or equal to about 2500 ppm.

[0136] For embodiments in which the ready-to-use heat transfer fluid includes zinc ion, the total amount of zinc ion may be greater than about 0.0001 ppm based on the total weight of the heat transfer fluid ready to use. Within this range, the amount of zinc ion can be less than about 30 ppm. Also within this range, the amount of zinc ion can be less than or equal to about 15 ppm.

[0137] For embodiments in which the ready-to-use heat transfer fluid includes nitrate, the total amount of nitrate may be greater than about 0.0001 ppm based on the total weight of the ready-to-use heat transfer fluid. Within this range, the amount of nitrate can be less than about 20,000 ppm. Also within this range, the amount of nitrate can be less than or equal to about 5000 ppm.

[0138] For embodiments in which the ready-to-use heat transfer fluid includes nitrite, the total amount of nitrite may be greater than about 0.0001 ppm based on the total weight of the ready-to-use heat transfer fluid. Within this range, the amount of nitrite can be less than about 20,000 ppm. Also within this range, the amount of nitrite can be less than or equal to about 5000 ppm.

[0139] For embodiments in which the ready-to-use heat transfer fluid includes molybdate, the total amount of molybdate may be greater than about 0.0001 ppm based on the total weight of the ready-to-use heat transfer fluid. Within this range, the amount of molybdate may be less than about 20,000 ppm. Also within this range, the amount of molybdate may be less than or equal to about 2000 ppm.

[0140] For embodiments in which the ready-to-use heat transfer fluid includes an azole compound, the total amount of azole compound can vary from about 0.005% by weight to about 2% by weight based on the total weight of ready-to-use heat transfer fluid. Within this range, the azole compound may be present in an amount greater than or equal to about 0.007% by weight or, in some embodiments, greater than or equal to about 0.01% by weight. Also within this range, the azole compound may be present in an amount of less than or equal to about 1.5% by weight or, in some embodiments, less than or equal to about 1% by weight.

[0141] For embodiments in which the ready-to-use heat transfer fluid includes copper and copper alloy corrosion inhibitor, the total amount of copper and copper alloy corrosion inhibitor may be greater than about 0.0001 ppm based on total weight of ready-to-use transfer fluid. Within this range, the amount of copper and copper alloy corrosion inhibitor may be less than about 10,000 ppm. Also within this range, the amount of copper and copper alloy corrosion inhibitor may be less than or equal to about 2500 ppm.

[0142] For embodiments in which the ready-to-use heat transfer fluid includes silicate, the total amount of silicate may be greater than about 0.0001 ppm based on the total weight of the ready-to-use heat transfer fluid. Within this range, the amount of silicate may be less than about 1000 ppm as Si. Also within this range, the amount of silicate may be less than or equal to about 600 ppm as Si.

[0143] For embodiments in which the ready-to-use heat transfer fluid includes silicate stabilizer, the silicate stabilizer may be present in an amount greater than about 0.0001 ppm based on the total weight of the heat transfer fluid. ready-to-use heat. Within this range, the amount of silicate stabilizer may be less than about 3000 ppm. Also within this range, the amount of silicate stabilizer may be less than or equal to about 800 ppm.

[0144] For embodiments in which the ready-to-use heat transfer fluid includes acrylate-based polymer, the total amount of acrylate-based polymer may be greater than about 0.0001 ppm based on the total weight of the fluid ready-to-use heat transfer system. Within this range, the amount of acrylate-based polymer may be less than about 5000 ppm. Also within this range, the amount of acrylate-based polymer may be less than or equal to about 1500 ppm.

[0145] The pH of the ready-to-use heat transfer fluid can be between about 6.8 and about 10.0 at room temperature. Within this range, the pH may be greater than or equal to about 7.5 or, in some embodiments, greater than or equal to about 7.8. Also within this range, the pH may be less than or equal to about 9.0 or, in some embodiments, less than or equal to about 8.8.

[0146] A method of preventing corrosion in accordance with the present teachings includes contacting a ready-to-use heat transfer fluid of a type described herein with a heat transfer system. The heat transfer system may include one or a plurality of components manufactured by controlled atmosphere brazing (i.e., CAB). In some embodiments, the heat transfer system may include aluminum.

[0147] It is also understood that in some applications, such as heavy-duty engines, it may be desirable to incorporate one or more additional corrosion inhibitors (e.g., including, but not limited to, nitrites, molybdates, and/or the like, their salts and combinations thereof).

[0148] Ready-to-use heat transfer fluids in accordance with the present teachings are further demonstrated by the non-limiting examples that follow. The following examples illustrate features in accordance with the present teachings and are provided by way of illustration only. They are not intended to limit the scope of the appended claims or their equivalents.

EXAMPLES

[0149] Three different tests were used to demonstrate the improved corrosion protection performance of heat transfer fluids in accordance with the present teachings compared to other heat transfer fluids. Test heat transfer fluid solutions (or coolants) were prepared by diluting a heat transfer fluid concentrate with deionized water to the desired concentrations of 25 vol% solutions. or 50% by vol. Additives (e.g., organophosphates, HEDP, phenyl phosphinic acid, calcium acetate monohydrate, magnesium acetate tetrahydrate, polyacrylates, etc.) were either added to the soda concentrates or added during the preparation of the P soda concentrate formulations. , Q and R shown in Table 6.

[0150] The radiator hub leaching test was used to compare and contrast the performance of the tested heat transfer fluids with respect to rapid passivation and reduced nitrite consumption when the test fluids are in contact with exchanger part surfaces. aluminum heat shields manufactured using the CAB technique. Two different types of radiators from two different models of newly introduced North American light duty vehicles were selected for testing. Radiators have bent tubes (type B tubes). The aluminum parts of the radiators were cut into cubes with approximate dimensions of 25 mm x 25 mm x 25 mm. The desired numbers (12 to 22) of radiator cubes were placed in either a new polypropylene bottle (500 mL or 1000 mL) or 453.592 gram (16 oz) glass bottle. 50% volume of pre-diluted heat transfer fluid test solution was added to the bottles with radiator cubes to fully cover the cubes. The bottles were then sealed tightly with a lid and placed in an oven at a temperature of 100° C for 14 days. At the end of the leaching test, the radiator cubes were removed and the upper portion of the test solution was sampled for analysis. The amount of heat transfer fluid solution and the numbers of radiator cubes used in the tests were selected so that the volume of test solution per gram of radiator cubes had values between about 9.5 mL/g and about 15 mL/g. A test condition with a smaller test solution volume per gram of radiator cube value corresponds to a more demanding test condition.

[0151] ASTM D4340 tests and anodic polarization curve measurements under GM9066P test conditions were used to measure and compare the performance of heat transfer fluids with respect to protecting molten aluminum against high temperature corrosion under heat transfer conditions heat rejection components, typically found in engine blocks and cylinder heads. The test setting used in anodic polarization measurements was the same as that specified in GM9066P. Test solutions contained 25 vol.%. of soda (diluted by deionized water) plus 100 ppm of NaCl chloride. A sand casting AA319 cut from an engine block was used as the working electrode. The surface temperature of the AA319 electrode was controlled at 130 ± 2°C during testing. The anodic polarization curve was obtained after the solution temperature had reached steady-state values (i.e., 102 ±2°C) for 5 to 6 hours using a scan rate of 2 mV/sec. ASTM D4340 tests were conducted in accordance with the latest ASTM D4340 specification.

[0152] Experimental data showing the benefits of using heat transfer fluids in accordance with the present teachings are summarized in Tables 4 to 19 below. Table 4 shows the compositions of A to H base heat transfer fluid concentrates (or coolant concentrators) used to prepare the heat transfer fluid solutions used in the tests. Table 5 shows the compositions of base I to N heat transfer fluid concentrates (or coolant concentrates) used to prepare the heat transfer fluid solutions used in the tests. Table 6 shows the P to R base heat transfer fluid concentrate compositions (or coolant concentrates) used to prepare the heat transfer fluid solutions used in the tests. Tables 7 to 10 show the results obtained in radiator cube leaching tests for Comparative Examples 1 to 12 using comparative heat transfer fluids as test solutions. Tables 11 to 18 show the results obtained in radiator cube leaching tests for Examples 1 to 30 using heat transfer fluids in accordance with the present teachings. Table 19 shows ASTM test results for comparative heat transfer fluid solutions (Comparative Examples 13 to 22) and heat transfer fluid solutions in accordance with the present teachings (Examples 31 to 51).

[0153] The results clearly show that refrigerants (or heat transfer fluids) containing organophosphates or phosphate esters (e.g., Triton H-66, Triton H-55, Cedephos FA-600, Chemfac NF-100, Chemfac NA-350, Chemfac PF-636, Butyl Acid Phosphate, Ethyl Hexyl Acid Phosphate, Isooctyl Acid Phosphate) in accordance with the present teachings provide substantially better corrosion protection performance than the corresponding fluids of the comparative examples which do not contain organophosphate.

[0154] Comparative Examples 2, 3 and 4 in Table 7 and Comparative Examples 11 and 12 in Table 10 show a nearly 100% reduction in nitrite in the absence of organophosphate for four different test refrigerants after 2 weeks of leaching test. radiator cube at 110° C. In contrast, in the presence of 0.025 wt% to 0.2 wt% organophosphates in the test coolants shown in the examples in Tables 11 to 18, the reduction in nitrite concentration in the test coolants after 2 weeks of radiator cube leaching test at 100°C was drastically reduced. In some cases, as shown in Example 11 (Table 13) and Examples 21 to 24 (Table 16), in the presence of Triton H-55 or Triton H-66 at a concentration between 0.05% by weight and 0.1% by weight by weight, the reduction in nitrite concentrations in the test coolants after 2 weeks of radiator cube leaching testing at 100°C was reduced to a level that was even better than that obtained in the test coolant containing inorganic phosphate, ions of calcium, magnesium and polyacrylate ions described in U.S. Patent No. 8,617,416 B1 (see Comparative Examples 1 in Table 7).

[0155] United States Patent Application Publication No. 2014/0061529 A1 describes a method for passivating the chemical reactivity of metal surfaces of heat exchangers with refrigerants in the presence of nitrites through the addition of 1-hydroxyethylidene-1 acid ,1-diphosphonic acid (HEDP), phenylphosphonic acid or phenylphosphinic acid. The addition of HEDP, phenylphosphonic acid, or phenylphosphinic acid to an engine coolant containing 2-ethyl hexanoic acid, sebacic acid, and tolyltriazole led to a reduction in nitrite consumption when the coolant was in contact with aluminum automotive heat exchangers. However, the improvement of passivation of welded aluminum surface covered with potassium fluoroluminate flux residue in the presence of organophosphates in test coolants in accordance with the present teachings was substantially better than that obtained using phenylphosphonate as described in the Publication of U.S. Patent Application No. 2014/0061529 A1 (cf. Comparative Examples 5 to 7 in Table 8; Comparative Examples 9 and 10 in Table 9; and Examples in Tables 11 to 18). The results in Table 19 show that the presence of the most effective refrigerant additive HEDP in the 9 different test refrigerant formulations as described in U.S. Patent Application Publication No. 2014/0061529 A1 (see also U.S. Patent Application Publication No. .2015/0267101 A1) led to very high molten aluminum AA329 corrosion rates under ASTM D4340 test conditions. These rates substantially exceeded the corrosion rate requirement of no more than 1.0 mg/cm2/week in ASTM D4340 testing per ASTM D3306, D6210, as well as the engineering standards of many automotive OEMs in carbon-based engine coolants. glycol for light duty and heavy duty.

[0156] In contrast, as shown in Table 19, test coolants in accordance with the present teachings containing organophosphates such as Triton H-66, Chemfac NF100 and Isooctyl acid phosphate provided much lower corrosion rates in ASTM D4340 tests than the test coolant solution containing HEDP and in addition satisfy the corrosion rate requirements of ASTM D3306 and D6210 on light-duty and heavy-duty glycol-based engine coolants. As shown in Table 19, some of the test coolants containing Chemfac NF-100, Triton H-66, Isooctyl acid phosphate, Chemfac NF-100 or Triton H-66 in concentration ranges in accordance with the present teachings provided corrosion rates. ASTM D4340 less than 0.1 mg/cm3/week (for example, see Examples 39 to 47 and Example 51 in Table 19).

[0157] The results shown in Tables 11 to 19 further indicate that organophosphate-containing refrigerants in accordance with the present teachings can not only provide superior corrosion protection and substantially reduced nitrite consumption when in contact with CAB aluminum heat exchanger surfaces, but also provide superior corrosion protection under the high heat rejection temperature conditions typically found in engine blocks and cylinder heads in engine cooling systems. For example, superior corrosion protection under high heat rejection temperature conditions can be observed in the presence of calcium ions and magnesium ions, or strontium ions and magnesium ions - with or without the additional presence of polyacrylate in a concentration range in accordance with the present teachings. Visual observations of the post-D4340 test samples for Examples 40 to 48 in Table 19 show that the metal surface had no signs of corrosion and remained bright in appearance and in new condition - thus, in accordance with the results of corrosion rate obtained from measuring weight loss in test samples. Table 4. AH Test Refrigerant Formulations Table 5. IN Test Refrigerant Formulations Table 6. PR Test Refrigerant Formulations

[0158] Figure 1 shows anodic polarization measurements obtained on an AA319 molten aluminum alloy electrode immersed in 25% vol. of refrigerant concentrate + 100 ppm chloride ions for 6 hours under heat rejection heat transfer conditions. The surface temperature of the AA319 electrode is 130° C. It can be seen that coolants P and R (Table 6) containing an organophosphate (Chemfac NF-100) provided substantially better corrosion protection for cutting molten aluminum AA319 from the block of 3.0-L vehicle engine than other coolants (i.e., Coolant E, Coolant E + 0.05 wt% HEDP sodium salt, Coolant D, and Coolant J) under the test conditions. As shown in Figure 1, the presence of HEDP in Refrigerant E resulted in a significant increase in corrosion of AA319 under high heat rejection temperature corrosion conditions, in accordance with the ASTM D4340 results shown in Table 19. In fact, the Results in Figure 1 show that Refrigerant E + 0.05 wt% HEDP sodium salt had the highest AA319 corrosion attack under the test conditions. Table 7. Radiator Hub Leach Test Results for Comparative Examples 1-4 Table 8. Radiator Cube Leaching Test Results for Comparative Examples 5-7 Table 9. Radiator Cube Leaching Test Results for Comparative Examples 8-10 Table 10. Radiator Cube Leaching Test Results for Comparative Examples 11-12 Table 11. Radiator Cube Leaching Test Results for Examples 1-4 Table 12. Radiator Cube Leaching Test Results for Examples 5-8 Table 13. Radiator Cube Leaching Test Results for Examples 9-12 Table 14. Radiator Cube Leaching Test Results 13-16 Table 15. Radiator Cube Leaching Test Results for Examples 17-20 Table 16. Radiator Cube Leach Test Results 21-24 Table 17. Radiator Cube Leach Test Results 25-28 Table 18. Radiator Cube Leaching Test Results for Examples 29-30 Table 19. ASTM D4340 Test Results

[0159] The contents in their entirety of each and every patent and non-patent publication mentioned herein are incorporated herein by reference, except in the case of any inconsistent description or definition of the present application, which description and definition shall prevail.

[0160] It should be understood that the indefinite articles "a" and "an" in reference to an element (e.g., a "freezing point depressant", "an organophosphate", "a carboxylic acid or a salt thereof" , "a component", etc.) do not exclude the presence, in some embodiments, of a plurality of such elements.

[0161] The above detailed description and accompanying drawings have been provided by way of explanation and illustration and are not intended to limit the scope of the appended claims. Many variations in the preferred embodiments illustrated herein will be apparent to one skilled in the art, and remain within the scope of the appended claims and their equivalents.

[0162] It should be understood that the elements and characteristics mentioned in the appended claims can be combined in different ways to produce new claims that likewise fall within the scope of the present invention. Thus, although appended dependent claims depend only on an independent or dependent claim, it must be understood that such dependent claims may alternatively be made to depend on the alternative of any previous claim - whether independent or dependent - and that such combinations must be understood as part of this application.

Claims (16)

1. Heat transfer fluid concentrate, characterized by the fact that it comprises: a freezing point depressant, water or a combination thereof; an organophosphate selected from the group consisting of ethylene glycol phosphate, 1,2,3-propanetriol phosphate, an ethoxylated phosphoric acid of C6 to C12 alkyl alcohol, an alkali metal salt of cresyl ethoxylate phosphate ester, cresyl phosphate potassium, octylphenoxypolyethoxyethyl phosphate, octylphenoxy polyethylene phosphate, polyethylene glycol mono(octylphenyl) ether phosphate, an aryl acid phosphate, alkali metal salts of an alkylphenoxypolyethoxyethyl phosphoric acid and combinations thereof; a carboxylic acid or a salt thereof; an alkaline earth metal ion; a water-soluble polymer; and a component selected from the group consisting of an alkali metal ion, a transition metal ion, an inorganic phosphate, molybdate ion, nitrate ion, nitrite ion, an azole compound, a copper corrosion inhibitor and copper alloy. copper, a silicate, a silicate stabilizer, and combinations thereof, wherein the heat transfer fluid concentrate is borate-free. 2. Fluid concentrate according to claim 1, characterized in that it further comprises an additional component selected from the group consisting of a phosphonate, a phosphinate, a dye, a biocide, an antifoam, a surfactant, a dispersant, a anti-particle deposition agent, a wetting agent, an additional corrosion inhibitor and combinations thereof. 3. Fluid concentrate according to claim 1, characterized in that the freezing point depressant comprises an alcohol; and optionally, wherein: (a) the alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, furfurol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethoxylated furfuryl alcohol, ethylene glycol, diethylene glycol, triethylene glycol , 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, butylene glycol, glycerol, glycerol-1,2-dimethyl ether, glycerol-1,3-dimethyl ether, glycerol monoethylether, sorbitol, 1,2 ,6-hexanetriol, trimethylolpropane, methoxyethanol and combinations thereof, or (b) the water is deionized water, demineralized water, softened water or a combination thereof. 4. Fluid concentrate according to claim 1, characterized by the fact that: (a) the carboxylic acid comprises one or a plurality of C6 to C20 carboxylic acids, and wherein each of the one or plurality of C6 acids the C20 carboxylic acid is individually selected from the group consisting of an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, an aromatic monocarboxylic acid, an aromatic dicarboxylic acid and combinations thereof; or (b) the carboxylic acid is selected from the group consisting of 2-ethyl hexanoic acid, heptonic acid, octanoic acid, nonanoic acid, adipic acid, decanoic acid, neodecanoic acid, sebacic acid, benzoic acid, p-toluic acid, t -butyl benzoic acid, an alkoxybenzoic acid and combinations thereof. 5. Fluid concentrate according to claim 1, characterized by the fact that the alkaline earth metal ion is: (a) selected from the group consisting of magnesium, calcium, strontium and a combination thereof; (b) derived from a water-soluble alkaline earth metal salt, an alkaline earth metal compound or a combination thereof; or (c) derived from an alkaline earth metal oxide. 6. Fluid concentrate according to claim 1, characterized in that the alkali metal ion is: (a) lithium; (b) derived from a water-soluble alkali metal salt, an alkali metal compound or a combination thereof; or (c) derived from an alkali metal oxide, such as lithium oxide. 7. Fluid concentrate according to claim 1, characterized in that the transition metal ion is: (a) zinc; (b) derived from a water-soluble transition metal salt, a transition metal compound or a combination thereof; or (c) derived from a transition metal oxide, such as zinc oxide. 8. Fluid concentrate according to claim 1, characterized by the fact that: (a) the phosphate comprises a phosphorous oxoacid and optionally wherein the phosphorous oxoacid is selected from the group consisting of phosphoric acid, sodium orthophosphate, sodium orthophosphate potassium and combinations thereof; (b) the azole compound is selected from the group consisting of benzotriazole, tolyltriazole, 4-methyl benzotriazole, 5-methyl benzotriazole, 1-butyl-1H-benzotriazole, mercaptobenzothiazole, thiazole, substituted thiazoles, imidazole, benzimidazole, substituted imidazoles, indazole, substituted indazoles, tetrazole, substituted tetrazoles, tetrahydrobenzotriazoles, tetrahydrogenated benzotriazoles, tetrahydrotolyltriazole, 4-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, tetrahydrobenzotriazole, alkali metal salts thereof and combinations thereof same; (c) the molybdate ion is derived from an alkali metal molybdate, an alkaline earth metal molybdate or a combination thereof; (d) the silicate comprises an alkali metal silicate; (e) the silicate stabilizer comprises a silicone; (f) the water-soluble polymer is a homopolymer, a copolymer, a terpolymer, a quadpolymer or a combination thereof; (g) the water-soluble polymer is a polycarboxylate, and optionally wherein the polycarboxylate is an acrylate-based polymer, an acrylate-based copolymer, an acrylate-based terpolymer, an acrylate-based quadpolymer, or a combination thereof same; or (h) the water-soluble polymer is an acrylate/acrylamide copolymer, a polymethacrylate, a polymaleic acid, a maleic anhydride-based polymer, a maleic acid-based polymer, a maleic acid-based copolymer, a terpolymer based on maleic acid, a modified acrylamide-based polymer, an acrylamide-based copolymer or an acrylamide-based terpolymer. 9. Fluid concentrate according to claim 1, characterized in that the pH of the heat transfer fluid concentrate at 50% concentration is between 6.8 and 10.0. 10. Heat transfer fluid concentrate according to claim 1, characterized by the fact that: the freezing point depressant comprises from 1% by weight to 99% by weight based on a total weight of the fluid concentrate heat transfer; the organophosphate comprises from 0.002% by weight to 5% by weight based on the total weight of the heat transfer fluid concentrate; the carboxylic acid or salt thereof comprises from 1% by weight to 10% by weight based on the total weight of the heat transfer fluid concentrate, wherein the carboxylic acid comprises one or a plurality of C6 to C20 carboxylic acids, and wherein the one or plurality of C6 to C20 carboxylic acids is individually selected from the group consisting of an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, an aromatic monocarboxylic acid, an aromatic dicarboxylic acid, and combinations of the same; calcium ion is present at a concentration of up to 200 mg/mL based on the total weight of the heat transfer fluid concentrate; Magnesium ion is present at a concentration of up to 150 mg/L based on a total weight of heat transfer fluid concentrate; an azole compound is present from 0.01 wt% to 3 wt% based on the total weight of the heat transfer fluid concentrate. 11. Fluid concentrate according to claim 10, characterized in that the water-soluble polymer further comprises: (a) the acrylate-based polymer; or (b) wherein the freezing point depressant is selected from the group consisting of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerol and combinations thereof. 12. Ready-to-use heat transfer fluid comprising the heat transfer fluid concentrate as defined in claim 1 and water, wherein the heat transfer fluid concentrate is present in an amount ranging from 40% by volume to 60% by volume based on a total volume of ready-to-use heat transfer fluid. 13. Method of preventing corrosion in a heat transfer system, characterized in that it comprises: contacting at least a portion of the heat transfer system with a ready-to-use heat transfer fluid formed from the heat transfer concentrate heat transfer fluid as defined in claim 1. 14. The method of claim 13, wherein: (a) the ready-to-use heat transfer fluid further comprises an azole compound, wherein the alkaline earth metal ion comprises calcium and magnesium ions and wherein the water-soluble polymer is an acrylate-based polymer; or (b) the heat transfer system portion comprises a component made by brazing in a controlled atmosphere. 15. Heat transfer fluid concentrate, characterized in that it is prepared by a process comprising a combination of (a) a freezing point depressant, (b) water, (c) an organophosphate selected from the group consisting of ethylene glycol, 1,2,3-propanetriol phosphate, a C6 to C12 alkyl alcohol ethoxylated phosphoric acid, an alkali metal salt of cresyl ethoxylate phosphate ester, potassium cresyl phosphate, octylphenoxypolyethoxyethyl phosphate, octylphenoxy and polyethylene, polyethylene glycol mono(octylphenyl)ether phosphate, an aryl acid phosphate, alkali metal salts of an alkylphenoxypolyethoxyethyl phosphoric acid and combinations thereof, (d) a carboxylic acid or a salt thereof and (and ) a water-soluble alkaline earth metal salt, an alkaline earth metal compound, an alkali metal oxide or a combination thereof, (f) a water-soluble polymer, and (g) a component selected from the group consisting of a salt water-soluble lithium, a lithium compound, a lithium oxide, a water-soluble zinc salt, a zinc compound, a zinc oxide, a water-soluble inorganic phosphate, a nitrate, a nitrite, a molybdate, an azole compound, a copper and copper alloy corrosion inhibitor, a silicate, a silicate stabilizer, a water-soluble polymer and combinations thereof, wherein the heat transfer fluid concentrate is borate-free; and optionally wherein the pH of the heat transfer fluid concentrate at 50% concentration is between 6.8 and 10.0. 16. Heat transfer fluid concentrate, characterized by the fact that it comprises: a freezing point depressant, water or a combination thereof; an organophosphate selected from the group consisting of an ethylene glycol phosphate, a polyether phosphate ester, 1, 2, 3-propanetriol phosphate, a combination thereof; a carboxylic acid or salt thereof; an alkaline earth metal ion; a water-soluble polymer; the component is selected from the group consisting of alkali metal ion, transition metal ion, an inorganic phosphate, a molybdate ion, nitrate ion, nitrite ion, an azole compound, a copper and copper alloy corrosion inhibitor, a silicate, a silicate stabilizer and combinations thereof.