WO2016203334A1 - Carbon nanotubes based hybrid automotive coolant - Google Patents
Carbon nanotubes based hybrid automotive coolant Download PDFInfo
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- WO2016203334A1 WO2016203334A1 PCT/IB2016/053253 IB2016053253W WO2016203334A1 WO 2016203334 A1 WO2016203334 A1 WO 2016203334A1 IB 2016053253 W IB2016053253 W IB 2016053253W WO 2016203334 A1 WO2016203334 A1 WO 2016203334A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/10—Liquid materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
Definitions
- the subject matter in general relates to coolant additives. More particularly, but not exclusively, the subject matter relates to dispersion of carbon nanotubes in coolant to enhance the functionality/properties of the coolant.
- Coolants have been widely used in automotive engines to prevent the engine from overheating, by transferring the heat generated within the engine.
- Traditional coolants used in an automotive vehicle may be a fluid such as water or ethylene glycol to which various additives were added to enhance the thermal heat transfer efficiency rate of the fluid.
- fluids have certain demerits.
- the nanoparticles dispersed in the base fluid may be a metal or metal oxide. It has been observed that, the use of metal nanoparticles in the base fluid may result in theproduction of insoluble corrosion products that may block the radiator and reduce the heat transfer rates. Furthermore, it had been observed that metal oxide particles like ⁇ 1 2 0 3 and Si0 2 may erode the seal of a radiator, thereby leading to leakage of the coolant due to their extreme hardness property.
- a composition may include carbon nanotubes and a base fluid.
- the carbon nanotubes are dispersed in the base fluid.
- the carbon nanotubes may be functionalized prior to dispersion in the base fluid.
- a method for preparing a composition may be prepared by subjecting carbon nanotubes to a ball milling process to reduce the length of the carbon nanotubes.
- the ball milled carbon nanotubes are oxidized to functionalize the carbon nanaotubes. Further, the oxidized carbon nanotubes are dispersed in a base fluid.
- FIGs. 1A- IB are graphs illustrating the variation of viscosity with change in temperature on dispersion of various concentration of CNTs in a base fluid diluted with water in the ratk>70:30 (water : base fluid) and 50:50 respectively;
- FIGs. 2A- 2B shows the effect of shear rate on a shear stress at a temperature of 55°C on dispersion of various concentration of CNTs in a base fluid diluted with water in the ratio 50:50 (water : base fluid) and 70:30 (water : base fluid) respectively;
- FIGs. 2C- 2D shows the effect of shear rate on the shear stress at a temperature of 90°C on dispersion of various concentration of CNTs in the base fluid diluted with water in the ratio 50:50 (water : base fluid) and 70:30 (water : base fluid) respectively;
- FIGs. 3 A - 3D are graphs illustrating the variation of thermal conductivity with temperature change on dispersion of CNTs in a base fluid diluted with water in the ratio 70:30 (water : base fluid) and 50:50 respectively; and [0013] FIGs.4A - 4B are graphs illustrating variation in cumulative weight loss within an exposure time on dispersion of CNTs in a base fluid diluted with water in the ratio 50:50 (water: base fluid) and 80:20 to determine the rate of erosion respectively.
- Embodiments relate to the field of coolant additives. More particularly, but not exclusively, embodiments may relate to dispersion of carbon nanotubes in the coolant to enhance the functionality /properties of the coolant.
- a composition which may be used as coolant for automotive engines.
- the composition disclosed may include carbon nanotubes, a hybrid coolant as a base fluid and a coupling agent.
- the carbon nanotubes used are reduced in length by a mechanical process.
- the carbon nanotubes so obtained are further oxidized for addition of functional groups on the surface of the carbon nanotubes.
- a coupling agent is mixed with the functionalized carbon nanotubes, prior to the dispersion of the carbon nanotubes in the base fluid. The coupling agent helps in stabilizing the dispersion of the carbon nanotubes in the base fluid.
- a composition including carbon nanotubes, a base fluid, and a coupling agent is provided.
- the composition disclosed has enhanced properties, which may include high thermal conductivity, anti corrosive properties, and cavitation erosion, among others.
- the composition may also be referred as a nanofluid.
- the carbon nanotubes (CNTs) used in the composition is a multi walled carbon nanotube (MWCNT). It shall be noted that a person skilled in the art may use others types of carbon nanotubes for example, single walled carbon nanotube (SWCNT) in the disclosed composition.
- the carbon nanotubes used in the composition are synthesized by a chemical vapour deposition method (CVD).
- CVD chemical vapour deposition method
- the CVD method is well known in the art, and therefore has not been described in detail. It shall be noted that, the carbon nanotubes may be synthesized by other process, such as arc discharge, laser ablation, flame synthesis, and high pressure carbon monoxide, among others.
- the multi walled carbon nanotubes with diameter 20 nm to 50 nm and length 10 microns to 25 microns are synthesized by the aforementioned process i.e. CVD method.
- the MWCNTs formed are of long length, which is undesirable.
- the long length of the MWCNTs may result in entanglement of the MWCNTs, thereby forming agglomerates in the base fluid.
- the formation of agglomerates in the base fluid may result in poor dispersion of the MWCNTs in the base fluid.
- the length of the MWCNTs is reduced prior to dispersion of the MWCNTs in the base fluid.
- the MWCNTs are subjected to a mechanical process.
- ball milling process is used to reduce the length of the MWCNTs.
- the ball milling process is performed for a time period ranging from 12 hours to 16 hours.
- the length of the MWCNTs is reduced to about 1 micron, after ball milling the MWCNTs. It shall be noted that, the ball milling process is not described in detail as the ball milling process is a well known process.
- Carbon nanotubes produced by the CVD method are hydrophobic in nature. Due to its hydrophobic nature, the MWCNTs are not soluble or less soluble in any solvent. Further, the MWCNTs may have poor adhesion to the base fluid. [0026] In an embodiment, MWCNTs are chemically modified to overcome the aforementioned problem. The MWCNTs are chemically modified by oxidation process. The oxidation of the MWCNTs facilitates the introduction of functional groups on the surface of the MWCNTs. The functional groups may include polar groups such as -COOH, and -OH groups, among others. The oxidized MWCNTs will be hydrophilic in nature, thereby facilitating improved solubility of the MWCNTs in the base fluid.
- the MWCNTs are oxidized after the MWCNTs are subjected to the ball milling process.
- the ball milled MWCNTs are oxidized in an acidic medium.
- the MWCNTs are refluxed in the acidic medium to carry out the oxidation process.
- the acidic medium may be a solution, which is a mixture of sulphuric acid and nitric acid in the ratio 4: 1.
- the MWCNTs are refluxed in the acidic medium for about 3- 4 hours at a temperature maintained between 107 °C and 108 °C.
- the time period to carry out the reflux process is restricted to the aforementioned range, as the oxidation of the MWCNTs for prolonged time period may damage the structure of the MWCNTs.
- other acids such as, perchloric acid may also be used to oxidise the MWCNTs.
- the solution of MWCNTs is washed with water to neutralize the pH of the solution.
- the solution is further filtered to separate the MWCNTs.
- the residual MWCNTs obtained after filtration is dried under vacuum conditions to get oxidized MWCNTs powder.
- dispersion of the oxidized MWCNTs in the base fluid may enhance the functionality or properties of the composition.
- the base fluid may include ethylene glycol, sebasic acid, tolyltriazole, sodium nitrite, and sodium hydroxide.
- the base fluid is prepared by mixing chemicals such as sebasic acid, tolyltriazole, sodium nitrite, and sodium hydroxide in ethylene glycol. Weighed quantity of the aforementioned chemicals are added in the weighed quantity of ethylene glycol and mixed thoroughly in a bath sonicator.
- chemicals such as sebasic acid, tolyltriazole, sodium nitrite, and sodium hydroxide in ethylene glycol. Weighed quantity of the aforementioned chemicals are added in the weighed quantity of ethylene glycol and mixed thoroughly in a bath sonicator.
- the base fluid may also be referred as a hybrid coolant.
- the base fluid may be composed of 90 - 95% of ethylene glycol, 2 - 5 % of sebasic acid, 0.05 - 0.3 % of tolyltriazole, 1 - 3 % of sodium nitrite, and sodium hydroxide to maintain the pH of the base fluid to about 8.5.
- the weight percent of carbon nanotubes to be dispersed in the base fluid may be between 0.025 and 0.1 % of the base fluid.
- the base fluid may be diluted with water.
- the base fluid may be diluted with water in the ratio 20:80 (base fluid: water), 30:70(base fluid: water), or 50:50 (base fluid: water).
- the base fluid may be used in automotives upon dilution with water.
- the base fluid may be diluted with water in the ratio 20 to 50:80 to 50 (base fluid: water).
- the composition may include a coupling agent. The coupling agent added to the composition helps in stabilizing the CNT's dispersion in the base fluid.
- Gum Arabic is used as a coupling agent.
- the addition of gum Arabic improves the adhesion behaviour of the CNTs with the base fluid.
- the amount of Gum Arabic used is based on the amount of CNTs being used.
- the amount of gum Arabic and CNTs used is in the ratio 1:1. Equal amount of gum Arabic and CNTs are mixed in water; the mixture so obtained is sonicated for about 45 minutes.
- the CNTs so obtained are dispersed in the base fluid.
- the CNTs so obtained are dispersed in the diluted base fluid.
- the composition may be prepared by dispersing a mixture of carbon nanotubes and the coupling agent in the base fluid using a physical agitation method.
- the agitation method facilitates the formation of a stable suspension of the carbon nanotubes in the base fluid.
- the physical agitation methods may include high shear mixing, such as with a high speed mixer, homogenizers, micro fluidizers, high impact mixing, and ultrasonication methods.
- the physical agitation method used is preferably ultrasonication.
- the mixture may be sonicated in a probe type sonicator at a frequency of 10 KHZ at a power level of 100 W.
- gum Arabic helps in improving the stability of the CNTs in the base fluid, however if the ratio of Gum Arabic exceeds the aforementioned ratio, it may result in the formation of large amount of foam, which is undesirable.
- the stability of the composition is measured using dynamic light scattering techniques in terms of changes in zeta potential.
- Zeta potential is a key indicator to determine the stability of colloidal suspension.
- Table 1 provided below shows an increase in the value of zeta potential after time span of two months, as compared to the value of zeta potential in the first day upon dispersion of CNTs in the base fluid. Further, the value of zeta potential also increases upon agitation.
- the stability of the composition is achieved by adding the coupling agent.
- a foaming tendency test as per ASTM D 1881 to check the foam break time for the composition was performed. From Table 2 provided below it has been observed that, the foam break time for the composition are within normal limits i.e. less than 5 seconds, and hence CNTs dispersed along with Gum Arabic is used for further analysis.
- FIGs 1A -IB are graphs showing a variation in viscosity with the change in temperature.
- a mixture of water and the base fluid without CNTs, in the ratio 50:50(water : base fluid) and 70:30(water : base fluid) were considered as a reference sample for the study.
- X axis represents temperature
- Y axis represents viscosity. From the graph plotted, it has been observed that, with an increase in the temperature, the viscosity decreases. Further, a moderate increase in the viscosity is observed when the mass fraction of the carbon nanotubes is more than 0.05%. Furthermore, the flow behaviour index of the composition is evaluated.
- FIGs 2A- 2B are graphs showing a variation of shear stress with shear rate for the CNTs dispersed base fluid(composition) at a temperature 55° C respectively.
- a mixture of water and the base fluid without CNTs in the ratio 50:50 (water : base fluid) and 70:30 ( water : base fluid) were considered as a reference sample for the study carried out at 55° C and 90°C.
- FIGs 2C- 2D are graphs showing a variation of shear stress with shear rate for the CNTs dispersed base fluid/composition at a temperature 90° C respectively.
- X axis represents the shear rate in seconds
- Y axis represents the shear stress in N/m . From the graphs plotted, it has been observed that, the shear stress and shear rate are varying almost linearly with intercept towards the origin, which is the characteristic of Newtonian fluids.
- a thermal analyzer KD2 pro had been used to measure the thermal conductivity of the CNTs dispersed base fluid.
- the thermal analyzer KD2 pro uses the transient line heat source method to measure the thermal conductivity. Further, the thermal conductivity was measured in the temperature range of -50°C to 150°C within an accuracy of 5 %.
- Graphs illustrated in FIGs 3A and 3B show an increase in the thermal conductivity of the CNTs dispersed base fluid. In this graph, the X axis represents temperature in Celsius, and Y axis represents the thermal conductivity in watts per meter kelvin ((W/ (m. K)).
- a mixture of water and the base fluid without CNTs, in the ratio 70:30 and 50:50 were considered as a reference sample for the study.
- T H i Temperature of water at inlet of radiator in °C
- T H 2 Temperature at outlet of radiator in °C
- A Heat transfer area in m 2
- Tci Temperature at inlet of air to radiator in °C
- Tc 2 Temperature of air at outlet of air in °C
- ⁇ Temperature difference
- lm logarithmic mean
- q heat transfer rate in W
- i Inside.
- Tables 3A- 3C and 3D- 3F represent test results for water: base fluid (70:30) and water: base fluid (50:50) in different velocities to evaluate the heat transfer coefficient.
- Table 3A Water: base fluid (70:30), velocity- 5m/s:
- Table 3B Water: base fluid (70:30), velocity - lOm/s:
- Table 3C Water: base fluid (70:30), velocity- 15m/s Ui Ui Ui Ui
- Table 3D Water: base fluid (50:50), velocity- 15m/s
- Table 3E Water: base fluid (50:50), velocity- lOm/s
- Table 3F Water: base fluid (50:50), velocity- 15m/s
- V represents velocity and Re represents Reynolds number. From the results presented in the above table, it may be concluded that, as the velocity and Reynolds number increases, the overall heat transfer coefficient decreases. However, it has been also observed that, the overall heat transfer coefficient increases as the weight fraction of the carbon nanotubes increases.
- Corrosion of metals present in an engine cooling systems by conventional coolants such as mixture of water and ethylene glycol is very common. Corrosion may result by an electrochemical or a chemical attack by agents that may be present in the surrounding atmosphere. Corrosion may result in disintegration of the surface and material loss due to either the conversion of the component metal into a less adherent material, or the dissolution of the material into the environment itself.
- various tests had been performed. The test performed includes glassware corrosion tests, corrosion of Cast Aluminium Alloys, and cavitation corrosion test.
- a) Glassware corrosion test as per ASTM D 1384 Glassware corrosion test was performed to analyse the corrosion inhibitive properties of the CNTs dispersed base fluid (composition). In this test, the corrosion inhibitive properties of the CNTs dispersed base fluid/ composition was evaluated for metals that may be present in engine cooling systems Viz., copper, solder, brass, cast iron, mild steel and aluminium. The metals disclosed were totally immersed in aerated CNTs dispersed base fluid/composition mixed with corrosive water for 336 hrs (14 days) at 88°C. Based on the weight change incurred by the metals, the corrosion inhibitive properties of the CNTs dispersed base fluid (composition) was evaluated.
- Each of the tables presented below represent the weight loss incurred by each of the metals, upon treating each of the metals with the CNTs dispersed base fluid.
- the base fluid used in the study is diluted with water in the ratio 80:20 (water: base fluid), 70:30, and, 50:50 and the analysis of the study is provided in Table 4A - 4C respectively.
- Heat transfer corrosion is reported in terms of weight loss of the test specimen during the test.
- the heat-transfer corrosion rate (R) is calculated as follows.
- R corrosion rate, mg/cm /week
- W b weight of test specimen before test in grams
- A heat-flux surface area inside O-ring, cm .
- Cavitation erosion test per ASTM G 32 code This test method is used to estimate the relative resistance of materials (specimen) to cavitation erosion. To determine the resistance to cavitation erosion, standard tests as per ASTM G-32 were conducted at a test frequency of 20 KHz. The cavitation erosion is measured in terms of weigh loss of the materials. In this method, the specimen was immersed in the base fluid dispersed with CNTs of various weight fractions. Further, face of the specimen was subjected to high frequency ultra-sonic waves for a predetermined time period (1 hr) also referred as exposure time. The test cycles were repeated for 10 hours in order to obtain a history of mass loss versus time (exposure time).
- FIGs.4A - 4B are graphs illustrating variance in cumulative weight loss within an exposure time on dispersion of CNT's in a base fluid diluted with water in the ratio 50:50 (water: base fluid) and 80:20 (water : base fluid), to determine the rate of erosion.
- X axis represents exposure time in hours
- Y axis represents cumulative weight loss in mg. From the graph, it has been observed that, the cumulative weight loss of the specimen increases as the exposure time of the specimen increases. It has also been observed that, there is an insignificant change in the weight loss incurred by the specimen, with the dispersion of CNT's in the base fluid.
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WO2003004944A2 (en) * | 2001-01-30 | 2003-01-16 | Materials And Electrochemical Research (Mer) Corporation | Nano carbon materials for enhancing thermal transfer in fluids |
US20130062555A1 (en) * | 2011-09-11 | 2013-03-14 | Acta Technology Inc | Nanofluids and a method of making nanofluids for ground source heat pumps and other applications |
US20140312263A1 (en) * | 2013-04-22 | 2014-10-23 | Uchicago Argonne, Llc | Advanced thermal properties of a suspension with graphene nano-platelets (gnps) and custom functionalized f-gnps |
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WO2003004944A2 (en) * | 2001-01-30 | 2003-01-16 | Materials And Electrochemical Research (Mer) Corporation | Nano carbon materials for enhancing thermal transfer in fluids |
US20130062555A1 (en) * | 2011-09-11 | 2013-03-14 | Acta Technology Inc | Nanofluids and a method of making nanofluids for ground source heat pumps and other applications |
US20140312263A1 (en) * | 2013-04-22 | 2014-10-23 | Uchicago Argonne, Llc | Advanced thermal properties of a suspension with graphene nano-platelets (gnps) and custom functionalized f-gnps |
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