ORGANIC HEAT TRANSFER SYSTEMS, METHODS, AND FLUIDS

Abstract

The disclosed technology relates to heat transfer fluids and heat transfer systems and methods using heat transfer fluids. In particular, the technology relates to heat transfer fluids containing heat transfer additives, such as, for example, phase change materials and / or halogenated hydrocarbons. The operation of a power source generates heat. A heat transfer system in communication with the power source regulates the generated heat to ensure that the power source operates at an optimal temperature. A heat transfer system generally includes a heat transfer fluid that facilitates the absorption and dissipation of heat from the power source. Conventional heat transfer fluids, generally consisting of water and glycol, tend to freeze and freeze.

Description

[Technical Field]

[0001] The disclosed technology relates to heat transfer fluids and heat transfer systems and methods using heat transfer fluids. Specifically, the technology relates to heat transfer fluids that contain heat transfer additives, such as, for example, phase change materials and / or halogenated hydrocarbons. [Background technology]

[0002] The operation of a power supply generates heat. A heat transfer system in communication with the power supply regulates the generated heat and ensures that the power supply operates at an optimal temperature. A heat transfer system generally includes a heat transfer fluid that facilitates the absorption and dissipation of heat from the power supply. Conventional heat transfer fluids, generally consisting of water and glycol, tend to freeze.

[0003] The promise of advanced immersion heat transfer fluids is based on thermally conductive, electrically non-conductive (dielectric) coolants. Full immersion helps reduce energy consumption and lower costs, but given the poor thermophysical properties (density, thermal conductivity, and heat capacity) of such fluids compared to water cooling, further improvements in the heat transfer performance of dielectric coolants are needed.

[0004] Therefore, there is a need for a heat transfer system and method that uses inexpensive heat transfer fluids with improved heat transfer performance. Summary of the Invention

[0005] Thus, the disclosed technology solves the heat transfer performance and safety concerns of cooling electrical components by operating the electrical components immersed in a heat transfer fluid containing a phase change material. The phase change material may or may not be in the form of some encapsulation. Surprisingly, it has been found that by fully encapsulating some phase change material in the form of well-dispersed nanodroplets in the heat transfer fluid, a highly durable heat transfer system with improved heat transfer performance can be achieved.

[0006] Similarly, improved heat transfer performance can be achieved by adding halogenated hydrocarbons to the heat transfer fluid.

[0007] Thus, a heat transfer fluid is provided that includes a hydrocarbon oil and a heat transfer additive. In one embodiment, the heat transfer additive can include a phase change material. In the same or a different embodiment, the heat transfer additive can include a halogenated hydrocarbon.

[0008] The method and / or system is particularly useful in transferring heat from battery systems, such as in electric vehicles and uninterruptible power supplies, or from computing electronics, such as in servers and digital asset mining devices.

[0009] The present technology also includes a method of lubricating an electrified driveline, the method including applying a heat transfer fluid to the driveline and operating the driveline.

[0010] The present technology also includes a method for cooling an electrical component, such as a computer server, that includes immersing the electrical component in a bath of heat transfer fluid and operating the electrical component.

[0011] Also provided herein is a submerged coolant system that can be used, for example, in an electric vehicle or a server farm or data center. The system can include a battery pack or computer server located in a vessel that is in fluid contact with a heat transfer fluid reservoir filled with the heat transfer fluid discussed herein.

[0012] The method and / or system also finds application in other electrical components such as, for example, aircraft electronics, other computer electronics, inverters, DC-DC converters, AC-DC converters, chargers, phase change inverters, electric motors, electric motor controllers, and DC-AC inverters. DETAILED DESCRIPTION OF THE INVENTION

[0013] Various preferred features and embodiments are described below by way of non-limiting example.

[0014] The disclosed technology provides a method for cooling electrical components by directly contacting or immersing the electrical components in a composition comprising a hydrocarbon (optionally isoparaffinic) oil and an oxygenate and operating the electrical components.

[0015] Electrical components include any electronic device that utilizes electrical power and generates thermal energy that must be dissipated to prevent the device from overheating. Examples include computer electronics such as aircraft electronics, computer servers and computer electronics (such as microprocessors), as well as computer hardware used in cryptocurrency mining, uninterruptible power supplies (UPS), power electronics (such as IGBTs, SCRs, thyristors, capacitors, diodes, transistors, rectifiers), energy storage devices, among others. Electrical components also include batteries and power delivery systems such as automobile charging stations. Further examples include inverters, DC-DC converters, AC-DC converters, chargers, phase-change inverters, electric motors, electric motor controllers, and DC-AC inverters.

[0016] Although some examples of electrical components have been provided, the heat transfer fluid can be used in any assembly or for any electrical component to provide improved heat transfer fluid with low temperature performance without significantly increasing the electrical conductivity and potential flammability of the mixture.

[0017] The present method and / or system is particularly useful for transferring heat from battery systems, such as those found in electric vehicles, including electric cars, trucks, and even electrified mass transit vehicles like trains or streetcars. A key component in electrified transportation is often a battery module, which may include one or more battery cells stacked relative to one another to form a battery module, which may be stacked together to form a battery pack. Heat may be generated by each battery cell during charging and discharging operations, or may be transferred to the battery cells during key-off conditions of the electrified vehicle as a result of relatively extreme (i.e., hot) ambient conditions. Therefore, the battery module includes a heat transfer system for thermally managing the battery module over a full range of ambient and / or operating conditions. In practice, operation of the battery module may occur during the use and drain of power from the battery module, such as during operation of the battery module or during charging of the battery module. A charging system, including an AC power source, regulator, charging cable, and fuses, may also generate heat, and the present method and / or system may be used therewith. With regard to charging, the use of a heat transfer fluid can enable charging of the battery modules to at least 75% of the total battery capacity being recovered in a period of less than 15 minutes.

[0018] Similarly, the electrical components in an electrified vehicle may include fuel cells, solar cells, solar panels, photovoltaic cells, etc. that require cooling by a heat transfer fluid. Such electrified vehicles may also include conventional internal combustion engines, such as in hybrid vehicles.

[0019] Electrified vehicles may also include electric motors as electrical components. Electric motors may be used anywhere along the vehicle driveline, for example, to operate the transmission, axles, and differentials. Such electric motors may be cooled by heat transfer systems that use heat transfer fluids.

[0020] The method may be used, for example, to lubricate a drivetrain including an electrified transmission and / or an electric motor.

[0021] The present methods and / or systems are also particularly useful for transferring heat from computer electronics such as computer servers, and from other computer electronics, including, but not limited to, motherboards, circuit boards, chips (CPUs, GPUs), microprocessors, densely packed servers in data centers, computers in distributed computing clusters, workstations in office buildings, medical imaging devices, electronic communication equipment in cellular networks, solar panels, game consoles, personal computers, consumer electronics, high power diode laser arrays, light emitting diode (LED) arrays, theater lighting systems, video projectors, directed energy weapons, and solar panels.

[0022] The method and / or system can include providing a heat transfer system for housing an electrical component requiring cooling. The heat transfer system includes, among other things, a reservoir in which the electrical component can be positioned in a manner that allows the electrical component to be in direct fluid contact with a heat transfer fluid. The reservoir is in fluid contact with a heat transfer fluid reservoir and a heat exchanger.

[0023] The electrical components may operate in conjunction with the operation of a heat transfer system, which may be operated by circulating a heat transfer fluid through the heat transfer system, for example, via pumping or via natural circulation.

[0024] For example, the heat transfer system may include means for pumping cooled heat transfer fluid from the heat transfer fluid reservoir to the vessel, pumping heated heat transfer fluid out of the vessel through a heat exchanger, and returning it to the heat transfer fluid reservoir. In some embodiments, the heat transfer system may use natural circulation to drive fluid flow. Natural circulation involves a flow in which density changes as a result of heat input, driving fluid flow by gravity. Thus, while the electrical components are operating, the heat transfer system may also operate to provide cooled heat transfer fluid to the electrical components to absorb heat generated by the electrical components and to remove heat transfer fluid heated by the electrical components and send it to the heat exchanger for cooling and recirculation to the heat transfer fluid reservoir.

[0025] The dielectric constant (also called the relative permittivity) is an important characteristic of heat-transfer fluids for immersion cooling systems. To avoid problems with current leakage, the heat-transfer fluid in which the electrical components are immersed can have a dielectric constant of 5.0 or less, as measured according to ASTM D924. The dielectric constant of the heat-transfer fluid at room temperature (i.e., 20-25°C) can also be less than 4.5, 4.0, 3.0, 2.5, or 2.3, or less than 1.9.

[0026] The heat transfer fluid may also have a kinematic viscosity, measured at 100°C, of ​​at least 0.7 cSt, or at least 0.9 cSt, or at least 1.1 cSt, or 0.7-7.0 cSt, or 0.9-6.5 cSt, or even 1.1-6.0 cS, as measured according to ASTM D445_100. For a given chemical family being pumped at a given power output, a higher viscosity fluid is typically less effective at removing heat given the higher resistance to flow. The same phenomenon also occurs for natural convection systems.

[0027] The immersion heat transfer fluid should be free-flowing at very low temperatures. In one embodiment, the heat transfer fluid has a pour point of at least -10°C, or at least -25°C, or at least -30°C, or at least -40°C, or at least -50°C, as measured according to ASTM D5985. In one embodiment, the heat transfer fluid may have an absolute viscosity of 900 cP or less at -30°C, or 500 cP or less at -30°C, or 100 cP or less at -30°C, as measured according to ASTM D2983.

[0028] The heat transfer fluid contains a hydrocarbon (possibly isoparaffinic) oil and an oxygenate.

[0029] The hydrocarbon (e.g., isoparaffinic) oil has a flash point, as measured according to ASTM D92 and / or ASTM D93, of at least 50°C, or at least 60°C, or at least 75°C, or at least 100°C, or at least 150°C, and in some cases at least 200°C, or at least 250°C.

[0030] Hydrocarbon oils [including isoparaffins (or isoparaffinic oils)] are saturated hydrocarbon compounds containing at least one hydrocarbyl branch or at least one saturated five- or six-membered hydrocarbyl ring sufficient to provide fluidity at both extremely low and high temperatures. The hydrocarbon oils (isoparaffins) of the present invention can include natural and synthetic oils, oils derived from hydrocracking, hydrogenation, and hydrofinishing of refined oils, re-refined oils, or mixtures thereof. Hydrocarbon oils include isoparaffinic oils (or isoparaffins), i.e., branched acyclic hydrocarbons, or cycloparaffinic oils (also called cycloparaffins, naphthenic oils).

[0031] Synthetic isoparaffin oils can be produced by the isomerization of primarily linear hydrocarbons to produce branched hydrocarbons. The linear hydrocarbons can be naturally occurring, synthetically prepared, or derived from a Fischer-Tropsch reaction or similar process. Isoparaffins can be derived from hydroisomerized wax, typically hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil can be prepared by a Fischer-Tropsch gas-to-liquid synthesis procedure, as well as other gas-to-liquid oils.

[0032] Suitable isoparaffins may be obtained from natural renewable sources. Natural (or bio-derived) oils refer to materials derived from renewable biological resources, organisms, or entities, and are distinct from materials derived from petroleum or equivalent sources. Natural sources of hydrocarbon oils include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters, such as fatty acid methyl esters (FAMEs). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other triglyceride sources include, but are not limited to, algae, tallow, and zooplankton. Linear and branched hydrocarbons may be obtained or extracted from vegetable oils and hydrofinished and / or hydroisomerized to produce isoparaffins in a manner similar to synthetic oils.

[0033] Another class of isoparaffin oils includes polyalphaolefins (PAOs). Polyolefins are well known in the art. In one embodiment, the polyolefins may be derived from olefins having 2 to 28 carbon atoms. By derivable or derived, it is meant that the polyolefin is polymerized from starting polymerizable olefin monomers or mixtures thereof having the recited number of carbon atoms. In embodiments, the polyolefins may be derived from olefins having 3 to 24 carbon atoms. In some embodiments, the polyolefins may be derived from olefins having 4 to 24 carbon atoms. In further embodiments, the polyolefins may be derived from olefins having 5 to 20 carbon atoms. In yet further embodiments, the polyolefins may be derived from olefins having 6 to 18 carbon atoms. In yet further embodiments, the polyolefins may be derived from olefins having 8 to 14 carbon atoms. In alternative embodiments, the polyolefins may be derived from olefins having 8 to 12 carbon atoms.

[0034] Often, the polymerizable olefin monomers include one or more of propylene, isobutene, 1-butene, isoprene, 1,3-butadiene, or mixtures thereof. An example of a useful polyolefin is polyisobutylene.

[0035] Polyolefins also include poly-α-olefins that can be derived from (or are derived from) α-olefins. α-olefins can be linear or branched, or mixtures thereof. Examples include monoolefins such as propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Other examples of α-olefins include 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and mixtures thereof. An example of a useful α-olefin is 1-dodecene. An example of a useful poly-α-olefin is polydecene.

[0036] Polyolefins may also be copolymers of at least two different olefins, also known as olefin copolymers (OCPs). These copolymers are preferably copolymers of α-olefins having from 2 to about 28 carbon atoms, preferably copolymers of ethylene and at least one α-olefin having from 3 to about 28 carbon atoms, typically copolymers of the formula CH2=CHR1, where R1 is a linear or branched alkyl radical containing from 1 to 26 carbon atoms. Preferably, R1 in the above formula can be an alkyl of 1 to 8 carbon atoms, more preferably an alkyl of 1 to 2 carbon atoms. Preferably, the olefin polymer is an ethylene-propylene copolymer.

[0037] When the olefin copolymer comprises ethylene, the ethylene content preferably ranges from 20 to 80 weight percent, more preferably from 30 to 70 weight percent. When propylene and / or 1-butene are used as comonomers with ethylene, the ethylene content of such copolymers is most preferably from 45 to 65 percent, although higher or lower ethylene contents can be present.

[0038] The hydrocarbon (e.g., isoparaffin) oil may be substantially free of ethylene and its polymers. The composition may be completely free of ethylene and its polymers. By substantially free, it is meant that the composition contains less than 50 ppm, or less than 30 ppm, or even less than 10 ppm, or 5 ppm, or even less than 1 ppm of a given material.

[0039] The hydrocarbon (e.g., isoparaffin) oil may be substantially free of propylene and its polymers. The hydrocarbon (e.g., isoparaffin) oil may be completely free of propylene and its polymers. The polyolefin polymers prepared from the aforementioned olefin monomers may have a number average molecular weight of 140 to 5000. The polyolefin polymers prepared from the aforementioned olefin monomers may also have a number average molecular weight of 200 to 4750. The polyolefin polymers prepared from the aforementioned olefin monomers may also have a number average molecular weight of 250 to 4500. The polyolefin polymers prepared from the aforementioned olefin monomers may also have a number average molecular weight of 500 to 4500. The polyolefin polymers prepared from the aforementioned olefin monomers may also have a number average molecular weight of 750 to 4000, as measured by gel permeation chromatography using polystyrene standards.

[0040] Isoparaffin oils can be saturated hydrocarbon compounds containing from 8 carbon atoms up to 50 carbon atoms and having at least one hydrocarbyl branch containing at least one carbon atom. In one embodiment, the saturated hydrocarbon compounds can have at least 10 or at least 12 carbon atoms. In one embodiment, the saturated hydrocarbon compounds can contain from 14 to 34 carbon atoms, provided that the longest continuous chain of carbon atoms is 24 carbons or less in length.

[0041] In an embodiment, the isoparaffinic oil has a longest continuous chain of carbon atoms that is 24 carbons or less in length.

[0042] In embodiments, the saturated hydrocarbon compound may be a branched acyclic compound having a molecular weight of 140 g / mol to 550 g / mol, or 160 g / mol to 480 g / mol, as measured by size exclusion chromatography (SEC) (SEC is also called gel permeation chromatography, GPC), liquid chromatography, gas chromatography, mass spectrometry, NMR, or a combination thereof.

[0043] Mineral oils often contain cyclic structures, i.e., cycloparaffins, also known as aromatics or naphthenes. In one embodiment, isoparaffins comprise saturated hydrocarbon compounds that are free or substantially free of cyclic structures. By substantially free, it is meant that the mineral oil contains less than 1 mol %, or less than 0.75 mol %, or less than 0.5 mol %, or even less than 0.25 mol % of cyclic structures. In some embodiments, the mineral oil is completely free of cyclic structures.

[0044] In an embodiment, the hydrocarbon oil may be a cycloparaffin oil (cycloparaffin). The cycloparaffin may be derived from a mineral oil. The cycloparaffin contains at least one saturated hydrocarbyl five- or six-membered ring. The cycloparaffin oil may contain at least 29 weight percent polycycloparaffins, i.e., two or more edge-sharing rings.

[0045] The hydrocarbon (e.g., isoparaffin) oil is the base compound of the heat transfer fluid. As such, the hydrocarbon (e.g., isoparaffin) oil constitutes the remainder of the composition after all oxygenates and other additives have been added. The hydrocarbon oil may be present in an amount of at least 60%, at least 70%, at least 80%, at least 90%, or at least 95% by weight of the composition. That is, the hydrocarbon oil may be present in an amount of 60-99%, or even 70-98.5%, or 80-98%, or 90-97, or 97.5% by weight. In some embodiments, the hydrocarbon oil may be present in an amount of 80-99%, or even 81-98.5%, or 82-98%, or 83-97%, or 84-97.5% by weight.

[0046] Oxygenate The composition may also include an oxygenate material that can act synergistically with the hydrocarbon (e.g., isoparaffin) oil to provide improved heat transfer, reduced kinematic viscosity, reduced low temperature viscosity, or increased flash point.

[0047] As used herein, oxygenate refers to organic (i.e., carbon-containing, also known as hydrocarbon) compounds that contain oxygen as one of their components. Oxygenate, as used herein, includes hydrocarbons having at least one aprotic or protic oxygen for every two carbon atoms, or every three carbon atoms, or every four carbon atoms, or every five carbon atoms, or every six carbon atoms. Oxygenates also include hydrocarbons having at least one aprotic or protic oxygen for every seven carbon atoms, or every eight carbon atoms, or every twelve carbon atoms. Oxygenates also include hydrocarbons having at least one aprotic or protic oxygen for every sixteen carbon atoms, or every twenty carbon atoms.

[0048] Oxygenates can include, for example, alcohols, ester oils, and ether oils. The oxygenate may be present in the heat transfer fluid at about 1 to about 45 wt. %, or in some cases, about 1.5 to about 40 wt. %, or about 2 to about 35 wt. The oxygenate may also be present in the heat transfer fluid at about 2.5 to about 30 wt. %, or about 3 to about 25 wt. In some embodiments, the oxygenate may be present in the heat transfer fluid at about 1 to about 20 wt. %, or in some cases, about 1.5 to about 19 wt. %, or about 2 to about 18 wt. The oxygenate may also be present in the heat transfer fluid at about 2.5 to about 17 wt. %, or 3 to about 16 wt.

[0049] Alcohols suitable for use in heat transfer fluids include monohydric alcohols, such as ethanol, methanol, propylene alcohol derivatives such as n-butanol and tert-butanol, and isopropyl alcohol. Higher branched alcohols include isomers of pentanol, hexanol, heptanol, octanol, decanol, dodecanol, tetradecanol, hexadecanol, and combinations thereof. Examples of branched alcohols include 2-ethylhexanol, isooctanol, isodecanol, and isododecanol. As used herein, alcohol also encompasses polyols, such as propylene glycol, ethylene glycol, 1,4-butanediol, pentaerythritol, and trimethylolpropane.

[0050] Ethers suitable for use as oxygenates in heat transfer fluids include those produced from petrochemical and renewable feedstocks. Examples include methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether (TAME), ethyl tertiary butyl ether (ETBE), and tertiary amyl ethyl ether (TAEE). Other examples of ethers include tert-hexyl methyl ether (THEME), dioctyl ether, and diisopropyl ether. Polyethers are also considered herein under the term "ether," including, for example, diethylene glycol dibutyl ether. Low molecular weight oligomers of polyalkylene glycols (i.e., polyalkylene oxides), including polyethylene glycol (PEG), polypropylene glycol (PPG), and mixed polymers thereof, may also be suitable. Polyethers include alkylene oxide polymers and oligomers containing 1 to 20 repeating units, or 2 to 10 repeating units, or 2 to 5 repeating units of ethylene oxide, propylene oxide, n-butylene oxide, or mixtures thereof. Suitable polyether compounds include 5,8,11,14-tetraoxaicosane, 1-(2-(2-butoxypropoxy)propoxy)propan-2-yl acetate, 2-(2-(2-(hexyloxy)ethoxy)ethoxy)ethyl oleate, 1-((1-((1-butoxypropan-2-yl)oxy)propan-2-yl)oxy)butane, 7,10,13,16,19-pentaoxaheptacosane, 2-(2-(2-(hexyloxy)ethoxy)ethoxy)ethyl 3,5,5-trimethylhexanoate, and combinations thereof.

[0051] The oxygenates can also be polyalkylene glycol esters by reacting polyalkylene glycols with fatty acids such as, for example, caprylic acid, myristic acid, palmitic acid, stearic acid, and the like.

[0052] In some cases, the oxygenate may be an alcohol or an ether and may be present in the heat transfer fluid at about 1 to about 45 weight percent, or in some cases, at about 1.5 to about 40 weight percent, or at about 2 to about 35 weight percent. Alcoholic or etheric oxygenates may also be present in the heat transfer fluid at about 2.5 to about 30 weight percent, or at about 3 to about 25 weight percent.

[0053] Ester oils suitable for use as oxygenates in heat transfer fluids include esters of monocarboxylic acids and monohydric alcohols, di-esters of diols and monocarboxylic acids and di-esters of dicarboxylic acids and monohydric alcohols, polyol esters of monocarboxylic acids, and polyesters of monohydric alcohols and polycarboxylic acids, and mixtures thereof. Esters can be broadly divided into two categories: synthetic and natural.

[0054] Synthetic esters suitable for use as oxygenates in heat transfer fluids may include esters of monocarboxylic acids (such as acetic acid, propionic acid, neopentanoic acid, 2-ethylhexanoic acid, and the like) and dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl and alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, linoleic acid, alkyl malonic acids, and alkenyl malonic acids) with any of a variety of monohydric alcohols (e.g., butyl alcohol, pentyl alcohol, neopentyl alcohol, hexyl alcohol, octyl alcohol, iso-octyl alcohol, nonyl alcohol, decyl alcohol, isodecyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, and propylene glycol). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, diecocyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid. Other synthetic esters include C5-C 12 Included are those made from monocarboxylic acids and polyols and polyol ethers, such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. The esters can also be monoesters of monocarboxylic acids and monohydric alcohols.

[0055] Suitable esters also include esters of hydroxy-substituted carboxylic acids, such as tartaric acid, malic acid, glycolic acid, and hydroxy fatty acids (eg, 12-hydroxystearic acid), in combination with monohydric alcohols, such as those listed above.

[0056] Natural (or bio-derived) esters refer to materials derived from renewable biological resources, organisms, or entities, and are distinct from materials derived from petroleum or equivalent sources. Suitable natural esters in heat transfer fluids include fatty acid triglycerides, hydrolyzed or partially hydrolyzed triglycerides, or transesterified triglyceride esters, such as fatty acid methyl esters (FAMEs). Suitable triglycerides include, but are not limited to, palm oil, soybean oil, sunflower oil, rapeseed oil, olive oil, linseed oil, and related materials. Other triglyceride sources include, but are not limited to, algae, tallow, and zooplankton.

[0057] In some cases, the oxygenate may be an ester, which may be present in the heat transfer fluid at about 1 to about 20 weight percent, or in some cases, at about 1.5 to about 19 weight percent, or at about 2 to about 18 weight percent. The ester oxygenate may also be present in the heat transfer fluid at about 2.5 to about 17 weight percent, or at 3 to about 16 weight percent.

[0058] heat transfer additives The heat transfer fluid may also include a heat transfer additive. One class of heat transfer additive is a phase change material. Phase change materials are known and are materials that absorb or release heat during a phase change, e.g., from solid to liquid and vice versa. Many types of phase change materials exist, including materials that change phase from solid to liquid over different temperature ranges. For example, a phase change material may include a material that changes from solid to liquid at 20°C to 200°C, i.e., a material that has a melting temperature of, e.g., 20°C to 80°C or 100°C to 200°C. Phase change materials may also include materials that have a melting temperature of, e.g., 30°C to 200°C, 40°C to 200°C, 20°C to 150°C, or 20°C to 100°C. Phase change materials may also include materials that have a melting temperature of, e.g., 30°C to 80°C, 40°C to 80°C, 20°C to 40°C, 30°C to 60°C, or 40°C to 50°C. Phase change materials can also include materials with melting temperatures, for example, between 100 and 200°C, or between 120 and 200°C, or between 100 and 175°C, or between 100 and 150°C. Those skilled in the art can readily determine the melting temperature of a substance using modulated differential scanning calorimetry (DSC). ASTM E793 is the standard test method for enthalpy of fusion and crystallization by differential scanning calorimetry, which can be used to determine melting temperatures. The specific method used herein involved placing a small sample (7-10 mg) in a pan inside the calorimeter along with a reference pan. The calorimeter is ramped from, for example, -80°C to approximately 80°C at a specified heating rate, e.g., 2 or 4°C / min. The temperature of the sample pan is compared to the reference pan while heat (energy) is applied until a phase change is observed. At this temperature, the measured temperature of the sample pan remains constant until the material completely changes phase, while the reference pan continues to increase in temperature. The temperature at which this occurs is the melting temperature, or more precisely, the phase change temperature. The particular phase change material for a particular application is selected depending on the thermal profile of the application and the desired heat absorption range. Combinations of phase change materials can be used to provide custom thermal gradients.Phase change materials include materials that (a) can change phase and remain suspended or miscible with oil, (b) contain blocks or side chains that change phase while other blocks or backbones remain miscible with oil, or (c) are encapsulated such that the encapsulant remains suspended while the phase change material absorbs or releases heat while changing phase.

[0059] Phase change materials can include, for example, paraffinic hydrocarbons, carboxylic acids, alcohols, and certain polymers.

[0060] Examples of paraffinic hydrocarbon phase change materials include those having about 17-30 carbon atoms, such as n-heneicosane, n-docosane, n-tricosane, and n-tetracosane. A table of example paraffinic hydrocarbons is provided below:

[0061] [Table 5]

[0062] In some embodiments, the paraffinic hydrocarbon may be a wax, which means less than one branch for every 10 carbons, or even less than one branch for every 20 carbons.

[0063] Examples of carboxylic acid phase change materials include lauric acid, myristic acid, tridecylic acid, methyl eicosanoate, and methyl behenate.

[0064] Examples of alcohol phase change materials include both phenol-type alcohols and fatty alcohols. Examples of phenolic compounds include phenol itself and substituted phenols such as 4-ethylphenol. Examples of fatty alcohols include 1-pentadecanol, cetyl alcohol, and 1-tetradecanol.

[0065] Polymers can also be used as phase change materials. For example, some polyethylene glycols ("PEGs"), such as PEG 1000, PEG 2000, and PEG 4000, as well as certain thermoplastics, have melting temperatures suitable for acting as phase change materials. Suitable polymers include poly(alpha)olefins, alpha olefin-maleic anhydride (AOMA) copolymers, maleic anhydride-styrene copolymers (MSC), poly(meth)acrylates (PMA), styrene-diene block copolymers (such as styrene-butadiene and / or styrene-isoprene block copolymers), polyurethanes, and polyesters, particularly polyesters of hydroxy-substituted fatty acids.

[0066] Acrylate and methacrylate (collectively referred to herein as (meth)acrylate) polymers and copolymers having one, two, or more blocks, in which at least one block undergoes a phase change, can also be used as phase change materials.

[0067] Such poly(meth)acrylate phase change materials can be prepared from a monomer mixture including (meth)acrylate monomers having alkyl groups of various lengths. The (meth)acrylate monomers can contain alkyl groups that are straight or branched chain groups or aromatic groups. The alkyl groups can contain 1 to 24 carbon atoms, for example, 1 to 20 carbon atoms. In some embodiments, poly(meth)acrylate phase change materials can be formed from monomers derived from saturated alcohols. In embodiments, poly(meth)acrylate phase change materials can be prepared from monomers derived from long-chain alcohol-derived groups.

[0068] Such poly(meth)acrylate polymer phase change materials can also include dispersant monomers. Dispersant monomers include monomers that can be copolymerized with (meth)acrylate monomers and contain one or more heteroatoms in addition to the carbonyl group of the (meth)acrylate. The dispersant monomers can contain nitrogen-containing groups, oxygen-containing groups, or mixtures thereof.

[0069] Such poly(meth)acrylates may be block copolymers or tapered block copolymers. In some embodiments, the poly(meth)acrylate copolymers may include block or tapered block poly(meth)acrylate polymers (P) having a first block (B1) that undergoes a phase change and is optionally substantially insoluble or insoluble in the hydrocarbon oil of the lubricating composition, and a second block (B2) that is substantially soluble or soluble in the hydrocarbon oil of the lubricating composition. The first block may include one or more monomers that undergo a phase change under the desired temperature conditions of the present invention to form a polymer that is optionally substantially insoluble in the base oil. These poly(meth)acrylate polymers are further taught in WO 2019 / 005738, published January 3, 2019, by Vincent et al., and are described in paragraphs

[0041] to

[0043] .

[0070] is incorporated herein by reference.

[0070] In some cases, the phase change material may include side chains that cause the material to change phase while the backbone of the material remains suspended or solubilized in the oil.

[0071] Some phase-change materials may require encapsulation in a heat-transfer fluid. The term "encapsulated" and its alternatives mean that the phase-change material is coated in some way with a polymer shell. In some cases, the encapsulating material may be used to encapsulate the phase-change material in a surfactant-type manner. In other instances, the phase-change material may include sufficient hydrophobic tails to surround or "encapsulate" itself. For example, (meth)acrylate polymers and copolymers may contain two or more blocks, at least one block undergoing a phase change and at least one block acting as an "encapsulant" for the phase-change block. Encapsulated phase-change materials are known in the art and are exactly what they sound like: a phase-change material encapsulated by an encapsulant. If a separate encapsulant material is required for the phase-change material, the encapsulant can include any known encapsulant for phase-change materials. Methods of encapsulation are well known in the art, and any method now known or later developed can be used to provide an encapsulant for a phase-change material. Methods can include, for example, chemical processes such as interfacial or in situ polymerization, physicochemical processes such as coacervation and phase separation, mechanical processes such as sol-gel encapsulation or solvent evaporation, and spray drying and coagulation, or one of several coating processes. Encapsulating agents can include, for example, surfactants, polymer shells, and inorganic encapsulating agents such as metal oxides.

[0072] In one embodiment, surfactant encapsulation of the phase change material can be produced by high shear emulsification using surfactant molecules. Surfactants are readily known to those skilled in the art, and one skilled in the art would be able to readily determine the best surfactant for preparing the encapsulated phase change material.

[0073] The polymerization encapsulation of the phase change material can be formed in situ by interfacial polymerization around emulsion droplets of the phase change material. Typical monofunctional polymer shells for encapsulation can be polystyrene, polymethylmethacrylate, melamine formaldehyde, or polyurethane.

[0074] Encapsulation of the phase change material by an inorganic material can be achieved, for example, by a metal oxide. In this method, a metal oxide shell can be formed in situ by hydrolysis around emulsion droplets of the phase change material. The metal oxide shell can be, for example, silica, alumina, or titania.

[0075] The encapsulation of the phase change material can help form a stable dispersion of the phase change material in the heat transfer fluid without rapidly increasing its viscosity. The high surface area-to-volume ratio of the encapsulated phase change material can increase the reaction rate of the phase change reaction. Ideally, the diameter of the encapsulated phase change material would be less than 1000 nm, or less than 750 nm, or less than 500 nm, or even less than 400 nm.

[0076] Phase change materials can be included in the heat transfer fluid at a concentration suitable to remove the desired amount of heat (Q) from the particular system under consideration. One skilled in the art, knowing how much heat is desired to be removed from the system, can readily determine such a concentration by determining or researching the specific latent heat (L) of the phase change material(s) and adding enough mass (m) of such phase change material(s) to absorb that heat according to the formula m = Q / L. Generally, phase change materials, as a single phase change material or combination of phase change materials, can be included in the heat transfer fluid at concentrations anywhere from 1% or even less to 50% or even more by weight of the heat transfer fluid. Phase change materials can also be included at 10 to about 48% by weight, or even about 20 to 45% by weight, or even about 25 to 42% by weight, or even 30 to 40% by weight.

[0077] Heat transfer additives for heat transfer fluids can also include halogenated hydrocarbons, which as used herein include halogenated ethers and halogenated amines. Halogenated hydrocarbons are hydrocarbons in which most of the hydrogen protons have been synthetically replaced by halogens. The halogen can be any halogen compound, but is often chlorine or fluorine, and is most often fluorine. Fluorinated hydrocarbons or fluorocarbons are known in the art and can include, for example, perfluoroalkenes, perfluoroalkanes, perfluoroethers, and perfluoroamines.

[0078] Any known halogenated hydrocarbon that is soluble in the heat transfer fluid can be used as the thermal additive. In embodiments, the halogenated hydrocarbon can be selected by selecting the boiling point of the halogenated hydrocarbon to be up to 5% lower than the flash point of the hydrocarbon oil. The boiling point of the halogenated hydrocarbon can be 5% lower to equal to the flash point of the hydrocarbon oil. In some embodiments, the boiling point of the halogenated hydrocarbon can be 2.5% lower to equal to the flash point of the hydrocarbon oil, or even 1% or 0.5% lower to equal to the flash point of the hydrocarbon oil.

[0079] The heat transfer fluid can include halogenated hydrocarbons in a wide range of amounts from 0.1 to 75 weight percent or more. Often, the halogenated hydrocarbons are included at lower concentrations of about 0.25 to 50 weight percent, or even 0.5 to 25 weight percent, or 1 to 10 weight percent, or even 1 to 5 weight percent. From a cost / benefit perspective, it has been found that halogenated hydrocarbons can provide benefits in the heat transfer fluids disclosed herein at concentrations of 0.1 to 5 weight percent, or even 0.25 to 4 weight percent, or 0.5 to 3 weight percent, or even 0.75 to 2 weight percent.

[0080] Another class of heat transfer additives includes, for example, metal particles and non-metal particles. The particles of the present invention are generally dispersed solids, often dispersed in the presence of one or more stabilizers or surfactants. The particles of the present invention are often submicron in size and are also called nanoparticles.

[0081] For metal nanoparticles, the metal of the metal nanoparticles can include alkaline earth metals, such as magnesium, calcium, strontium, and barium.

[0082] The metal of the metal nanoparticles can include transition metals such as scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, and cadmium.

[0083] The metal of the metal nanoparticles can include metals of the lanthanide series or actinide series, such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium, protactinium, and uranium.

[0084] The metal of the metal nanoparticles can include post-transition metals, such as aluminum, gallium, indium, thallium, tin, lead, bismuth, and polonium.

[0085] The metal of the metal nanoparticles can include metalloids such as boron, silicon, germanium, and antimony.

[0086] In certain embodiments, the metal may include aluminum. In embodiments, the metal may include iron. The metal may also include ruthenium. The metal may include cobalt. The metal may include rhodium. The metal may include nickel. The metal may include palladium. The metal may include platinum. The metal may include silver. The metal may include gold. The metal may include cerium. The metal may include samarium. The metal may include tungsten.

[0087] The metal nanoparticles may be present in their pure form or as oxides, carbides, nitrides, or mixtures or combinations of any of these materials.

[0088] For example, the metal nanoparticles can be iron oxide (e.g., Fe2O3, Fe3O4), cobalt oxide (e.g., CoO), zinc oxide (e.g., ZnO), cerium oxide (e.g., CeO2), and titanium oxide (e.g., TiO2). Boron oxide (e.g., BO3) is another metal nanoparticle that can be used. Aluminum oxide (e.g., AI2O3) is another metal nanoparticle that can be used. Magnesium oxide (e.g., MgO) is another metal nanoparticle that can be used. Tungsten oxide (e.g., W2O3, WO2, WO3, W2O5) is another metal nanoparticle that can be used.

[0089] Examples of metal carbide metal nanoparticles can include iron carbide (e.g., Fe3CH4), cobalt carbide (e.g., CoC, Co2C, Co3C), zinc carbide (e.g., ZnC), cerium carbide (e.g., CeC2), and titanium carbide (e.g., TiC). Boron carbide (e.g., BC) is another metal nanoparticle that can be used. Aluminum carbide (e.g., Al4C3) is another metal nanoparticle that can be used. Tungsten carbide (e.g., WC) is another metal nanoparticle that can be used.

[0090] Examples of metal nitride nanoparticles include iron nitrides (e.g., Fe2N, Fe3N4, Fe4N, Fe7N3, Fe 16Examples of metal nanoparticles that may be used include titanium nitride (e.g., ZnN), cobalt nitride (e.g., CoN, CoN, CoN), zinc nitride (e.g., ZnN), cerium nitride (e.g., CeN), and titanium nitride (e.g., TiN). Boron nitride (e.g., BN) is another metal nanoparticle that may be used. Aluminum nitride (e.g., AlN) is another metal nanoparticle that may be used. Tungsten nitride (e.g., WN, WN, WN2) is another metal nanoparticle that may be used.

[0091] The nanoparticles may also include non-metallic nanoparticles. Such non-metallic nanoparticles may be in the form of oxides, carbon, carbides, nitrides, or any mixture or combination of these materials. For example, the non-metallic nanoparticles may be graphene oxide or diamond.

[0092] The nanoparticles may have a D50 particle size of less than 1000 nm. In some embodiments, the nanoparticles may have a D50 particle size of less than 700 nm. The nanoparticles may have a D50 particle size of less than 500 nm. The nanoparticles may have a D50 particle size of less than 250 nm. The nanoparticles may have a D50 particle size of less than 100 nm. The nanoparticles may have a D50 particle size of less than 75 nm. The nanoparticles may have a D50 particle size of less than 50 nm. The nanoparticles may have a D50 particle size of 0.01 nm to 1000 nm. The nanoparticles may also have a D50 particle size of 0.1 nm to 100 nm. The nanoparticles may have a D50 particle size of 1 nm to 75 nm. The nanoparticles may have a D50 particle size of 10 nm to 50 nm. D50 particle size can be measured by dynamic light scattering according to ASTM E2490-09(2015).

[0093] The nanoparticles may have an average aspect ratio of 1 to 5,000. As used herein, "average aspect ratio" refers to the average ratio of the length of a particle in a nanoparticle mixture to the width of a particle in the mixture. The term "average" is intended to mean that any and all aspect ratios are possible, but that the average aspect ratio across the entire collection is within the disclosed range. The measurement method for determining the average aspect ratio length and width is not important, as long as the same measurement method is used for both measurements. The nanoparticles may also have an average aspect ratio of 1 to 2,500. The nanoparticles may also have an average aspect ratio of 1 to 1,000. The nanoparticles may also have an average aspect ratio of 1 to 500. The nanoparticles may also have an average aspect ratio of 1 to 250. The nanoparticles may also have an average aspect ratio of 1 to 100. The nanoparticles may also have an average aspect ratio of 1 to 50. The nanoparticles may also have an average aspect ratio of 1 to 25. The nanoparticles may also have an average aspect ratio of 1 to 10. The nanoparticles may also have an average aspect ratio of 10 to 5000. The nanoparticles may also have an average aspect ratio of 25 to 5000. The nanoparticles may also have an average aspect ratio of 50 to 5000. The nanoparticles may also have an average aspect ratio of 100 to 5000. The nanoparticles may also have an average aspect ratio of 250 to 5000. The nanoparticles may also have an average aspect ratio of 500 to 5000. The nanoparticles may also have an average aspect ratio of 1000 to 5000. The nanoparticles may also have an average aspect ratio of 2500 to 5000.

[0094] Generally, the nanoparticles are selected to have a thermal conductivity greater than that of the heat-transfer fluid. In some embodiments, the heat-transfer fluid may include particles having a minimum thermal conductivity greater than 5 W / mK. In some embodiments, the heat-transfer fluid may include nanoparticles having a thermal conductivity of 10 W / mK or greater. In some embodiments, the heat-transfer fluid may include nanoparticles having a thermal conductivity of 30 W / mK or greater. In some embodiments, the heat-transfer fluid may include nanoparticles having a thermal conductivity of 250 W / mK or greater. In some embodiments, the heat-transfer fluid may include nanoparticles having a thermal conductivity of 500 W / mK or greater. In some embodiments, the heat-transfer fluid may include nanoparticles having a thermal conductivity of 1000 W / mK or greater. As used herein, thermal conductivity may be measured by ASTM D7896-19.

[0095] The heat transfer fluid may include at least one nanoparticle at a concentration of 0.5 to 30 wt. % based on the weight of the heat transfer fluid. In some embodiments, the heat transfer fluid may include at least one nanoparticle at a concentration of 0.75 to 25 wt. %. In some embodiments, the heat transfer fluid may include at least one nanoparticle at a concentration of 1 to 20 wt. %. In some embodiments, the heat transfer fluid may include at least one nanoparticle at a concentration of 1.25 to 15 wt. %. In some embodiments, the heat transfer fluid may include at least one nanoparticle at a concentration of 1.5 to 10 wt. %.

[0096] However, care should be taken when administering nanoparticles so as not to exceed the dielectric constant constraints of the heat transfer fluid. Generally, this is not an issue unless more electrically conductive nanoparticles, such as nanoparticles in the form of pure metals, are used at high levels, generally 10% by weight or more. If there is concern, the heat transfer fluid can be formulated and the dielectric constant of the dispersion tested.

[0097] The nanoparticles are often administered with a surfactant suitable for binding the nanoparticles and keeping them dispersed in the heat transfer fluid, as will be readily apparent to one skilled in the art, and may include any surfactant or dispersant now known or later developed.

[0098] In one embodiment, the heat transfer fluid may include a hydrocarbon oil, one or more polyether oxygenates, and one or more metallic or non-metallic particles.

[0099] Performance Additives The heat transfer fluid may also include a performance additive package that balances the volume resistivity and electrical conductivity of the fluid. The performance additive package may include metal-containing detergents and dispersants.

[0100] The heat transfer fluid may further include a metal-containing detergent.

[0101] The metal-containing detergent may be an overbased detergent, a non-overbased detergent, or a mixture thereof. Typically, the detergent is overbased.

[0102] The metal-containing detergent may be a non-overbased detergent (sometimes referred to as a neutral detergent). The TBN of the non-overbased metal-containing detergent may be from 20 to less than 200, or from 30 to 100, or from 35 to 50 mgKOH / g. The TBN of the non-overbased metal-containing detergent may also be from 20 to 175, or from 30 to 100 mgKOH / g. When the non-overbased metal-containing detergent is prepared from a strong acid such as a hydrocarbyl-substituted sulfonic acid, the TBN may be lower (for example, from 0 to 50 mgKOH / g, or from 10 to 20 mgKOH / g).

[0103] As used herein, quoted values ​​of TBN and related TBN ranges are "as is," i.e., including conventional amounts of diluent oil, which typically range from 30% to 60% (often 40% to 55%) by weight of the detergent component.

[0104] The metal-containing detergent may be, for example, an overbased detergent having a TBN of more than 200 mgKOH / g (typically 250 to 600, or 300 to 500 mgKOH / g).

[0105] Overbased metal-containing detergents may be formed by the reaction of a basic metal compound with an acidic detergent substrate, which may include an alkyl aromatic sulfonic acid (such as an alkyl naphthalene sulfonic acid, an alkyl toluene sulfonic acid, or an alkyl benzene sulfonic acid), an alkyl salicylic acid, or mixtures thereof.

[0106] The basic metal compound is used to provide basicity to the detergent. The basic metal compound is a compound of a metal hydroxide or oxide. The metal of the metal-containing detergent may be, for example, an alkali metal or alkaline earth metal such as zinc, sodium, calcium, barium, or magnesium. Typically, the metal of the metal-containing detergent may be sodium, calcium, or magnesium.

[0107] In one embodiment, the metal-containing detergent may be a sulfonate, or mixtures thereof, which may be prepared from mono- or dihydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl) sulfonic acids, where the hydrocarbyl groups may contain 6 to 40, or 8 to 35, or 9 to 30 carbon atoms.

[0108] The hydrocarbyl groups may be derived from polypropylene or linear or branched alkyl groups containing at least 10 carbon atoms. Examples of suitable alkyl groups include branched and / or linear decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl, or mixtures thereof.

[0109] In one embodiment, the hydrocarbyl-substituted sulfonic acid is polypropene benzene sulfonic acid and / or C 16 ~C 24 alkyl benzene sulfonic acids, or mixtures thereof.

[0110] In one embodiment, the metal sulfonate detergent may be a predominantly linear alkyl benzene sulfonate detergent having a metal ratio of at least 8. In some embodiments, the linear alkyl group may be attached to the benzene ring at any position along the linear chain of the alkyl group, but often at the 2-, 3-, or 4-position of the linear chain, sometimes predominantly at the 2-position.

[0111] When neutral or slightly basic, the metal sulfonate detergents may have a TBN of less than 100, or less than 75, typically from 20 to 50 mg KOH / g, or from 0 to 20 mg KOH / g.

[0112] If overbased, the metal sulfonate detergent may have a TBN of greater than 200, or from 300 to 550, or from 350 to 450 mg KOH / g.

[0113] Phenate detergents are typically derived from p-hydrocarbylphenols, or generally alkylphenols. These types of alkylphenols can be sulfur-coupled and overbased, aldehyde-coupled and overbased, or carboxylated to form salicylate detergents. Suitable alkylsalicylates include those alkylated with propylene oligomers, butene oligomers, especially n-butene tetramers and pentamers, and with alpha-olefins, isomerized alpha-olefins, and polyolefins such as polyisobutylene.

[0114] Metal-containing detergents may be overbased. Overbased detergents are known in the art. Overbased materials, also called overbased salts or super-overbased salts, are generally single-phase, homogeneous Newtonian systems characterized by a metal content in excess of the amount that should be present for neutralization based on the stoichiometry of the metal and the particular acidic organic compound reacting with that metal. Overbased materials are prepared by reacting an acidic material (typically an inorganic acid or a lower carboxylic acid, preferably carbon dioxide) with a mixture containing an acidic organic compound, at least one inert organic solvent for the acidic organic material (mineral oil, naphtha, toluene, xylene, etc.), a stoichiometric excess of a metal base, and a promoter such as calcium chloride, acetic acid, phenol, or alcohol. The acidic organic material typically has a sufficient number of carbon atoms to provide solubility in oil. The amount of excess metal is generally expressed in terms of the metal ratio. The term "metal ratio" refers to the ratio of the total equivalents of the metal to the equivalents of the acidic organic compound. Neutral metal salts have a metal ratio of 1. A salt with 4.5 times the metal present in a normal salt has a metal excess of 3.5 equivalents, or a ratio of 4.5. The term "metal ratio" is also explained in the standard text "Chemistry and Technology of Lubricants," Second Edition, Edited by R.M. Mortier and S.T. Orszulik, Copyright 1997.

[0115] Overbased metal-containing detergents may be, for example, sulfur-free phenates, sulfur-containing phenates, sulfonates, salixarates, salicylates, and mixtures thereof, or their borated equivalents. The overbased detergents may be borated with a borating agent such as boric acid.

[0116] Overbased metal-containing detergents may also include "hybrid" detergents formed with mixed surfactant systems containing phenate and / or sulfonate components, such as phenate / salicylate, sulfonate / phenate, sulfonate / salicylate, sulfonate / phenate / salicylate, etc. For example, if a hybrid sulfonate / phenate detergent could be used, this hybrid detergent would be considered equivalent in amount to separate phenate and sulfonate detergents incorporating similar amounts of phenate soap and sulfonate soap, respectively.

[0117] Typically, the overbased metal-containing detergent may be a zinc, sodium, calcium, or magnesium salt of a phenate, sulfur-containing phenate, sulfonate, salixarate, or salicylate. Overbased salixarates, phenates, and salicylates typically have a total base number of 180 to 450 TBN. Overbased sulfonates typically have a total base number of 250 to 600, or 300 to 500. Overbased detergents are known in the art. In one embodiment, the sulfonate detergent may be a predominantly linear alkylbenzene sulfonate detergent having a metal ratio of at least 8. Predominantly linear alkylbenzene sulfonate detergents may be particularly useful for helping improve fuel economy.

[0118] Typically, the overbased metal-containing detergent may be a calcium or magnesium overbased detergent, such as a calcium sulfonate or magnesium sulfonate detergent.

[0119] The detergent may be present in the heat transfer fluid at 10 ppm to 5000 ppm, 25 ppm to 4000 ppm, 50 ppm to 3000 ppm, 100 ppm to 2000 ppm, 50 ppm to 500 ppm.

[0120] The dispersant (also called a surfactant) may be a succinimide dispersant, a Mannich dispersant, a succinamide dispersant, a succinate ester, an amide, or an ester-amide, or a mixture thereof. In one embodiment, the dispersant may be present as a single dispersant. In one embodiment, the dispersant may be present as a mixture of two or three different dispersants, where at least one may be a succinimide dispersant. In an embodiment, the heat transfer fluid may include both a succinimide dispersant and a polyolefin succinate ester dispersant.

[0121] The succinimide dispersant may be derived from an aliphatic amine, a polyamine, a hydroxy-substituted amine, or a mixture thereof. The aliphatic polyamine may be an aliphatic polyamine such as an ethylene polyamine, a propylene polyamine, a butylene polyamine, or a mixture thereof. In one embodiment, the aliphatic polyamine may be an ethylene polyamine. In one embodiment, the aliphatic polyamine may be selected from the group consisting of ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, polyamine distillation bottoms, and mixtures thereof.

[0122] The succinimide dispersant may be derived from an aromatic amine, an aromatic polyamine, or a mixture thereof. The aromatic amine may have one or more aromatic moieties linked by a hydrocarbylene group and / or a heteroatom. In certain embodiments, the aromatic amine may be a nitro-substituted aromatic amine. Examples of nitro-substituted aromatic amines include 2-nitroaniline, 3-nitroaniline, and 4-nitroaniline (typically 3-nitroaniline). The succinimide dispersant may be derived from 4-aminodiphenylamine or a mixture thereof.

[0123] In one embodiment, the dispersant may be a succinate ester, amide, or ester-amide. For example, the polyolefin succinate ester may be a polyisobutylene succinate ester of pentaerythritol, or a mixture thereof. The polyolefin succinate ester-amide may be polyisobutylene succinic acid reacted with an alcohol (such as pentaerythritol) and an amine (a diamine, typically diethylenetriamine).

[0124] In one embodiment, the dispersant may be a hydrocarbyl succinate ester or ester-acid mixture. The hydrocarbyl group may be a branched or linear hydrocarbyl group having from 8 to 60 carbon atoms. In one embodiment, the hydrocarbyl succinate ester may be a C10 to C22 hydrocarbyl succinate. Examples include decyl succinate, dodecyl succinate, tetradecyl succinate, hexadecyl succinate, octadecyl succinate, and combinations thereof. The succinate ester may be derived from an aliphatic alcohol, an aliphatic polyol, an amine-substituted aliphatic alcohol, and combinations thereof. Suitable alcohols include N,N-dimethylethanolamine, propanediol, trimethylolpropane, and pentaerythritol.

[0125] The dispersant may be an N-substituted long-chain alkenyl succinimide. An example of an N-substituted long-chain alkenyl succinimide is polyisobutylene succinimide. Typically, the polyisobutylene from which the polyisobutylene succinic anhydride is derived has a number average molecular weight of 350 to 5,000, or 550 to 3,000, or 750 to 2,500.

[0126] Dispersants may be post-treated by conventional methods by reaction with any of a variety of agents. Among these are boron compounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids such as terephthalic acid, hydrocarbon-substituted succinic anhydrides, maleic anhydride, nitriles, epoxides, and phosphorus compounds. In one embodiment, the post-treated dispersant is borated. In one embodiment, the post-treated dispersant may be reacted with a dimercaptothiadiazole. In one embodiment, the post-treated dispersant may be reacted with phosphoric acid or phosphorous acid.

[0127] The boron post-treated dispersant may be present in an amount to deliver 0 to 500 ppm of boron to the composition, or 5 to 250 ppm of boron to the composition, or 10 to 150 ppm of boron, or 20 to 100 ppm of boron.

[0128] Polyalkenyl Dispersants - PIB Dispersants - Succinate Esters, Amides or Imides - Esters with 3-40mgKOH / g TAN (oil-free) of 5-30, 6-20

[0129] The dispersant may be present from 20 ppm to 10,000 ppm, from 50 ppm to 8000 ppm, from 100 ppm to 6000 ppm, from 200 ppm to 4000 ppm.

[0130] In embodiments, the ratio of dispersant to metal-containing detergent may be from 4:1 to 1:2, or from 3:1 to 1:2, or from 2:1 to 1:2, or from 3:1 to 1:1, or from 2:1 to 1:1, by weight.

[0131] The heat transfer fluid may also include ashless antioxidants, more specifically sulfur-free antioxidants such as aminic and / or phenolic antioxidants.

[0132] The amine-based antioxidants include aromatic amines, such as those of the following formula:

[0133] [ka] (In the formula, R 5 is a phenyl group, a naphthyl group, or R 7 R can be an aromatic group such as a phenyl group substituted by 6 and R 7 can independently be hydrogen or an alkyl group containing 1 to 24, or 4 to 20, or 6 to 12 carbon atoms. In one embodiment, the aromatic amine antioxidant is an alkylated diphenylamine, such as nonylated diphenylamine of the formula:

[0134] [ka] Or it may contain a mixture of di-nonylated and mono-nonylated diphenylamine.

[0135] The phenolic antioxidant may be a hindered phenolic antioxidant in which one or both of the ortho positions on the phenol ring may be occupied by a bulky group such as t-butyl.

[0136] [ka] (In the formula, R 4 is an alkyl group containing 1 to 24 or 4 to 18 carbon atoms, and a is an integer of 1 to 5, or 1 to 3, or 2. The phenol may be a butyl-substituted phenol containing two or three t-butyl groups, for example, as shown below:

[0137] [ka]

[0138] The para position may also be occupied by a hydrocarbyl group or a group bridging two aromatic rings. In certain embodiments, the para position may be occupied by, for example, a group of the formula:

[0139] [ka] (In the formula, R 3 is a hydrocarbyl group such as an alkyl group containing 1 to 18, or 2 to 12, or 2 to 8, or 2 to 6 carbon atoms, where t-alkyl can be t-butyl).

[0140] In one embodiment, the heat transfer fluid includes an ashless antioxidant. In one embodiment, the ashless antioxidant is a sulfur-free antioxidant. In one embodiment, the ashless antioxidant is an aminic antioxidant. In another embodiment, the ashless antioxidant is a phenolic antioxidant. Mixtures of antioxidants may also be used.

[0141] The total amount of antioxidant may be 0.01 to 5 weight percent, or 0.15 to 4.5 weight percent, or 0.2 to 4 weight percent, or 0.05 to 1 weight percent, or 0.1 to 0.8 weight percent, or 0.15 to 0.6 weight percent of the heat transfer fluid.

[0142] The heat transfer fluid may also include a rheology modifier, such as, for example, a high molecular weight polymer. In one embodiment, the polymer may be prepared by polymerizing an alpha-olefin monomer, or a mixture of alpha-olefin monomers, or a mixture comprising ethylene and at least one C3 to C28 alpha-olefin monomer, in the presence of a catalyst system comprising at least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and an alumoxane compound.

[0143] Suitable polymers of the olefin polymer class include ethylene propylene copolymers, ethylene-propylene-alpha olefin terpolymers, ethylene-alpha olefin copolymers, ethylene propylene copolymers further containing a non-conjugated diene, and isobutylene / conjugated diene copolymers, each of which may then be provided with grafted carboxyl functionality.

[0144] Ethylene-propylene or higher alpha monoolefin copolymers may consist of 15 to 80 mole percent ethylene and 20 to 85 mole percent propylene or higher monoolefins, in some embodiments the molar ratios are 30 to 80 mole percent ethylene and 20 to 70 mole percent of at least one C3 to C10 alpha monoolefin, for example, 50 to 80 mole percent ethylene and 20 to 50 mole percent propylene. Terpolymer versions of the foregoing polymers may contain up to 15 mole percent non-conjugated dienes or trienes.

[0145] In these embodiments, the polymer substrate, such as an ethylene copolymer or terpolymer, can be an oil-soluble, substantially linear, rubbery material. Also, in certain embodiments, the polymer can be other than substantially linear, i.e., a branched or star polymer. The polymer can also be a random copolymer or a block copolymer, including diblock and higher order blocks, tapered blocks, and various other structures. These types of polymer structures are known in the art, and their preparation is within the capabilities of one skilled in the art.

[0146] The polymers of the disclosed technology can typically have a number average molecular weight (by gel permeation chromatography, polystyrene standard) that can be 2,000 to 500,000, 10,000 to 300,000, 50,000 to 250,000, or 9,000 to 55,000, or 11,000 to 52,000, or 40,000 to 50,000.

[0147] Another useful class of polymers is constituted by polymers prepared by cationic polymerization of, for example, isobutene or styrene. Typical polymers from this class include polyisobutenes obtained by polymerization of a C4 refinery stream having a butene content of 35 to 75% by weight and an isobutene content of 30 to 60% by weight in the presence of a Lewis acid catalyst such as aluminum trichloride or boron trifluoride, with aluminum trichloride being preferred. A suitable monomer source for producing poly-n-butenes is a petroleum feedstream such as Raffinate II. These feedstocks are disclosed in the art, such as U.S. Pat. No. 4,952,739. Polyisobutylene is a suitable polymer for the present invention because it is readily available from butene streams by cationic polymerization (e.g., using AlCl or BF catalysts).

[0148] It is known that polyisobutylene can be prepared by cationic polymerization using boron halides, specifically boron trifluoride (EP 206756, U.S. Pat. No. 4,316,973, GB 525542 and GB 828367). The polymerization of isobutylene can be controlled to obtain polyisobutylene with number average molecular weights (Mn) much higher than 1,000,000.

[0149] In one embodiment, the olefin polymer is a copolymer of olefins having 4 or more carbon atoms. In one embodiment, the olefin polymer (polyolefin) comprises 50 to 100 weight percent of units derived from at least one olefin monomer having 4 or more carbon atoms. In a typical embodiment, the olefin can be an unsaturated aliphatic hydrocarbon such as butene, isobutylene (or isobutene), butadiene, isoprene, or a combination thereof.

[0150] The polyolefin polymers of the present invention can have a number average molecular weight (gel permeation chromatography, polystyrene standard) of 20,000 to 10,000,000, 100,000 to 1,500,000, or 200,000 to 1,000,000. In other embodiments, the olefin polymer is polyisobutylene having a number average molecular weight of at least 50,000, at least 100,000, or at least 250,000, up to 850,000, 600,000, or 500,000. Specific ranges include 250,000 to 750,000 or 250,000 to 500,000.

[0151] The polymer may be present in the heat transfer fluid at 0.001 to 1%, or 0.003 to 0.8%, or 0.005 to 0.5%, or 0.01 to 0.1%, or 0.02 to 0.05%, for example, 0.003 to 0.1%, or even 0.003 to 0.01%, by weight. In another embodiment, the polymer additive may be present in the heat transfer fluid at a concentration of 500 ppm (parts per million) or less, or 300 ppm or less, or 100 ppm or less, or 10 ppm to 50 ppm, or even 20 to 40 ppm. The concentration of the polymer in the heat transfer fluid is measured on an oil-free basis.

[0152] Other conventional additives, such as antioxidants, corrosion inhibitors, fluoroelastomer seal regenerators, lubricity additives, flow improvers, or any combination thereof, may also be present. The additional additives may be present in amounts of 0.01 to 2 weight percent, or 0.025 to 2 weight percent, or 0.05 to 1 weight percent, or 0.075 to 0.5 weight percent of the composition.

[0153] Various embodiments of the compositions disclosed herein may optionally include one or more additional performance additives. These additional performance additives may include one or more flame retardants, smoke suppressants, antioxidants, flame retardants, metal deactivators, flow additives, corrosion inhibitors, foam inhibitors, demulsifiers, pour point depressants, seal swell agents, and any combination or mixture thereof. Typically, a fully formulated heat transfer fluid may contain one or more of these performance additives and often may contain multiple performance additive packages. In one embodiment, the one or more additional additives may be present at 0.01 weight percent to 3 weight percent, or 0.05 weight percent to 1.5 weight percent, or 0.1 weight percent to 1.0 weight percent.

[0154] The thermal management system disclosed herein can remove heat at a rate that allows for rapid charging of the battery. Fast charging targets include 120-1000 kW. The resulting heat generated during charging and discharging of the battery can generate over 10 kW of heat within the pack.

[0155] The thermal management systems disclosed herein can remove heat at a rate that allows for cooling of a CPU chip or process node. CPU chip operation can generate over 350 watts of heat from a single chip, up to 2 kW per process node.

[0156] The thermal management systems disclosed herein can lubricate a drivetrain, including, for example, a transmission or an electric motor, without electrostatic discharge.

[0157] The heat captured by the fluid may be recaptured and reused for other functional uses, such as heating the interior of a building or vehicle.

[0158] As used herein, the term "hydrocarbyl" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the remainder of the molecule and having predominantly hydrocarbon character. "Predominantly" means either A) some amount of the carbon atoms along the group backbone may be substituted with heteroatoms, for example, 1 in 5 or 1 in 10, or 1 in 15, or 1 in 20, or B) some amount of the carbon atoms along the group backbone may contain side chains containing heteroatoms, for example, 1 in 5 or 1 in 10, or 1 in 15, or 1 in 20. Examples of hydrocarbyl groups include: Hydrocarbon substituents, i.e., aliphatic (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic, aliphatic, and alicyclic-substituted aromatic substituents, as well as cyclic substituents in which the ring is completed through another portion of the molecule (e.g., two substituents together form a ring); Substituted hydrocarbon substituents, i.e., substituents containing non-hydrocarbon groups which, in the context of this invention, do not alter the predominantly hydrocarbon character of the substituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and sulfoxy); Hetero substituents, i.e., in the context of this invention, include substituents that have predominantly hydrocarbon character but contain other than carbon in a ring or chain otherwise composed of carbon atoms, and include substituents such as pyridyl, furyl, thienyl, and imidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. There may be no more than two, or no more than one non-hydrocarbon substituent for every 10 carbon atoms in the hydrocarbyl group; alternatively, there may be no non-hydrocarbon substituents in the hydrocarbyl group.

[0159] It is known that some of the materials described above may interact in the final formulation, so that the components of the final formulation may differ from those originally added. For example, metal ions (e.g., from detergents) may migrate to other acidic or anionic sites on other molecules. The products formed thereby, including the products formed upon using the compositions of the present invention in their intended applications, may not be easily described. Nevertheless, all such modifications and reaction products are included within the scope of the present invention. The present invention encompasses compositions prepared by mixing the components described above.

[0160] The present invention, which is useful for cooling electrical components during operation, can be better understood with reference to the following examples. [Example]

[0161] A series of phase change additives were prepared and evaluated for their ability to enhance heat absorption in oil-based fluids. The phase change materials include paraffinic hydrocarbons, summarized below (Table 1).

[0162] [Table 1]

[0163] Paraffinic hydrocarbons are encapsulated within a formaldehyde-bonded melamine resin coating. The encapsulated paraffin waxes were obtained from Microtek as MPCM 37D and MPCM 43D. These materials were evaluated for their thermal properties as received, as well as their effect on temperature-dependent viscosity (Table 2).

[0164] [Table 2] 1. Microtek Laboratories Inc. MPCM 43D 2. Nextek 57 from 3. Kinematic viscosity at 40°C is 42.7 m 2 / s, and the kinematic viscosity at 60°C is 19.5m 2 / s Group II base oil

[0165] The thermal properties of suspensions of phase-change materials in oil-based thermal fluids were determined by differential scanning calorimetry (DSC). DSC is used to measure the heat flow of a sample as a function of temperature. Modulated DSC subjects the sample to a linear heating method superimposed with sinusoidal temperature oscillations (modulation). Cyclic heating allows for the separation of the total heat flow into reversible and irreversible (dynamic) heat flows. MDSC analyses for this report were performed on a TA Instruments Model Q2000 DSC equipped with an RCS90 rapid cooling system. Samples were prepared in open aluminum Tzero™ DSC crucibles (approximately 6–8 mg of sample).

[0166] The sample was equilibrated at -60°C under a stream of nitrogen. The temperature was adjusted to plus / minus 0.53°C every 50 seconds and then increased at 4°C per minute to 75°C. The sample was held at 75°C for 0.5 minutes, then the temperature was ramped at -4°C per minute until it reached -60°C. After a 1 minute isothermal hold, the heating temperature cycle was repeated to 80°C.

[0167] Formulated thermal fluids were prepared as summarized below (Table 3). In addition to the paraffinic hydrocarbon and ether base oils, these fluids contained other performance additives with low treat rates, such as organic antioxidants. Additionally, the fluids contained 10 weight percent dispersed magnesium oxide, which was added to balance the density of the test fluid with that of the encapsulated wax particles.

[0168] [Table 3] 1. Oil formulation normalized to 100% 2. Kinematic viscosity at 40°C is 2.52 m 2 / g of paraffinic hydrocarbons 3. Kinematic viscosity at 40°C is 1.45m 2 / g of paraffinic hydrocarbons 4. Overbased calcium alkylbenzene sulfonate (TBN 300 mg KOH / g, 12 wt% calcium, 42% oil) 5. Ester of N,N-dimethylethanolamine and hexadecylsuccinic acid

[0169] The encapsulated wax particles were added to the above fluids, and the resulting suspensions were evaluated for phase change behavior by utilizing modulated DSC (Table 4).

[0170] [Table 4]

[0171] As shown, both samples exhibited an endothermic event consistent with a phase change. The magnitude of the heat of fusion was consistent with a 5% dilution of the material in the thermal fluid.

[0172] Each of the documents mentioned above is incorporated herein by reference, including any prior application to which priority is claimed, whether or not specifically listed above. The citation of any document is not an admission that such document qualifies as prior art or constitutes general knowledge to one of ordinary skill in the art in any jurisdiction. Except in the examples or where otherwise expressly indicated, all numerical values ​​in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, should be understood to be modified by the word "about." It should be understood that the upper and lower limits of amounts, ranges, and ratios set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements.

[0173] As used herein, the transitional term "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. However, in each occurrence of "comprising" herein, the term is also intended to encompass, as alternative embodiments, the phrases "consisting essentially of" and "consisting of," where "consisting" excludes any unspecified element or step, and "consisting essentially of" permits the inclusion of additional, unrecited elements or steps that do not materially affect the essential or basic and novel characteristics of the composition or method under consideration.

[0174] While certain representative embodiments and details have been shown for the purpose of illustrating the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, which in this regard should be limited only by the claims that follow.

Claims

1. A heat transfer fluid comprising a hydrocarbon oil and a heat transfer additive, wherein the heat transfer additive includes a phase change material.

2. The heat transfer fluid according to claim 1, wherein the phase change material is present in an amount of 1 to 50% by weight.

3. The heat transfer fluid according to claim 1, wherein the phase change material includes a paraffinic hydrocarbon having a melting temperature of 30 to 60°C.

4. The heat transfer fluid according to claim 1, wherein the phase change material comprises a carboxylic acid having a melting temperature of 30 to 60°C.

5. The heat transfer fluid according to claim 1, wherein the phase change material comprises a phenol or fatty alcohol having a melting temperature of 30 to 60°C.

6. The heat transfer fluid according to claim 1, wherein the phase change material includes a polymer material having a melting temperature of 30 to 60°C.

7. The heat transfer fluid according to claim 1, wherein the phase change material is enclosed by an encapsulating agent containing a surfactant.

8. The heat transfer fluid according to claim 1, wherein the phase change material is enclosed by an encapsulating agent containing a polymer shell.

9. The heat transfer fluid according to claim 1, wherein the phase change material is enclosed by a encapsulant containing a metal oxide shell.

10. The heat transfer fluid according to claim 1, wherein the heat transfer additive further comprises a halogenated hydrocarbon.

11. The heat transfer fluid according to claim 9, wherein the boiling point of the halogenated hydrocarbon is between 5% below and equal to the flash point of the hydrocarbon oil.

12. The heat transfer fluid according to claim 9, wherein the halogenated hydrocarbon includes a fluorocarbon.

13. The heat transfer fluid according to claim 9, wherein halogenated hydrocarbons are present in an amount of 0.1 to 25% by weight.

14. A method for lubricating an electrified drive line, comprising applying the heat transfer fluid described in claim 1 to the drive line.

15. A method for cooling an electrical component, comprising immersing the electrical component in a tank containing a heat transfer fluid as described in claim 1, and operating the electrical component.

16. The method according to claim 15, wherein the electrical component is a battery pack.

17. The method according to claim 15, wherein the electrical component is a computer server.

18. An immersion coolant system comprising electrical components located in a tank, wherein the tank is in fluid contact with a heat transfer fluid reservoir containing the heat transfer fluid described in claim 1.

19. The system according to claim 18, wherein the electrical component is a battery pack.

20. The system according to claim 18, wherein the electrical component is a computer server.