Deicing or anti-icing composition comprising diol-based compound and silane-based compound, and deicing or anti-icing method using same

Abstract

The present invention relates to a deicing or anti-icing composition comprising a diol-based compound and a silane-based compound, and a deicing or anti-icing method using the same, and more particularly, to a deicing or anti-icing composition comprising a diol-based compound and a silane-based compound, the composition having an excellent effect of delaying snow adhesion and icing when applied to the surface of a target object (metal material), and a deicing or anti-icing method using the same. Therefore, the deicing agent can be effectively used for deicing or anti-icing of the surface of a railway vehicle.

Description

Technical Field

[0001] This invention was completed with the support of the Ministry of Land, Infrastructure and Transport of South Korea. Its project inherent number is 1615012838, and its detailed project number is 22RTRP-B146023-05. The research management agency of the project is the Korea Institute of Science, Land, Infrastructure and Transport, the research project name is "Railway Technology Research Project", and the research topic name is "Development of a De-icing System for High-Speed Railway Vehicles". The competent authority is the Korea Railroad Corporation, and the research period is April 23, 2018 to December 31, 2022.

[0002] This patent application claims priority from Korean Patent Application No. 10-2022-0180629 filed on December 21, 2022, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.

[0003] The present invention relates to a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound, and a deicing or anti-icing method using the same. More particularly, the present invention relates to a deicing or anti-icing technology using a composition to which 0.5-1.0 wt% of an ethoxysilane-based compound based on propylene glycol (PG) is added. Background Art

[0004] During winter high-speed rail travel, snow and ice formed on the undercarriage and bogies of high-speed trains can cause the trains to sway and fall at high speed onto gravel sections of the trackbed, scattering debris. As mentioned above, this flying debris has repeatedly damaged railroad structures and facilities.

[0005] The primary cause of window breakage on railway vehicles in winter is also related to the accumulation of snow and ice on the underside of the vehicles. Among the physical damage caused by this winter's snow and ice, high-speed rail vehicle windows experience the most damage, along with damage to axle protection materials, track components, signal safety devices, and running gear components. This damage indirectly impacts vehicle operations and maintenance, including train delays, increased maintenance costs, and reduced safety.

[0006] In addition to damage caused by flying debris from accumulated snow and ice on the bottom of high-speed rail vehicles, train delays and reduced component function caused by freezing of rail vehicle doors, freezing of residual water in brake systems, and ice on exposed electrical equipment continue to occur. Therefore, disaster prevention and response technologies based on winter de-icing and anti-icing are needed.

[0007] In order to solve the above problems, although railway operating units have independently formulated emergency countermeasures from the perspective of operation and maintenance (such as stone debris prevention nets, slowed operation, and manual vehicle de-icing), they are inefficient.

[0008] Currently, when frozen or iced railway vehicles (such as the Nuriro, ITX-Sinchon, ITX-Chunchun, and Mugunghwa trains), de-icing relies on manual labor within the station yard. For high-speed vehicles (such as the KTX-1, KTX-Sancheon, SR, and Honam and Wongang lines), mobile hot air blowers are used. However, de-icing takes a long time, resulting in low energy efficiency and requiring excessive manpower only temporarily during winter. Therefore, there is a need for an effective chemical de-icing and anti-icing technology to replace these methods.

[0009] Previous research evaluated the ice-melting properties of various deicing fluid materials to identify a propylene glycol-based deicing fluid suitable for spray systems. Deicing fluid is sprayed to melt frozen snow and ice. The larger the frozen area, the longer it takes to melt. Therefore, pre-spraying deicing fluid on high-speed train vehicles to minimize snow adhesion can further improve thawing efficiency.

[0010] However, even when deicing fluid is sprayed on high-speed trains, it virtually disappears from the bogie surface during high-speed operation, failing to prevent snow from adhering to it, thus reducing anti-icing performance. To address this degradation of anti-icing performance during high-speed operation, the use of hydrophobic agents has been investigated. Recently, research is underway to develop anti-icing functional surfaces that utilize super-hydrophobic surfaces to prevent snow accumulation and ice formation. Summary of the Invention Problems to be solved by the present invention

[0011] The present inventors have thus confirmed that a composition comprising a glycol-based deicing fluid and a silane-based water repellent has a superior deicing or anti-icing effect compared to conventional compositions.

[0012] Therefore, an object of the present invention is to provide a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound.

[0013] Another object of the present invention is to provide a deicing or anti-icing method, the method comprising the step of applying a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound to a surface of a target object.

[0014] Another object of the present invention is to provide a deicing or anti-icing use of a composition comprising a glycol-based compound and a silane-based compound. Means used to solve problems

[0015] The present invention relates to a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound, and a deicing or anti-icing method using the same. Compared with existing deicing fluids, the composition of the present invention exhibits superior deicing or anti-icing performance.

[0016] The present inventors prepared a deicing or anti-icing composition comprising propylene glycol (PG) and 0.5-1.0 wt% of fluoroethoxysilane or aminoethoxysilane, and confirmed that the composition has excellent effects on preventing snow adhesion and delaying ice formation.

[0017] Hereinafter, the present invention will be described in more detail.

[0018] One aspect of the present invention is a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound.

[0019] In the present invention, the composition may include 50.0-90.0 wt% of the diol-based compound and 0.1-2.0 wt% of the silane-based compound with respect to the entire composition.

[0020] Preferably, the composition may contain 50-85wt%, 50-80wt%, 50-75wt%, 50-70wt%, 55-90wt%, 55-85wt%, 55-80wt%, 55-75wt%, 55-70wt%, 60-90wt%, 60-85wt%, 60-80wt%, 60-75wt%, 60-70wt%, 65-90wt%, 65-85wt%, 65-80wt% or 65-75wt% of the diol-based compound relative to the total composition, for example, it may contain 65-70wt%, but is not limited thereto.

[0021] Preferably, the composition may contain 0.1-1.8wt%, 0.1-1.5wt%, 0.1-1.2wt%, 0.1-1.0wt%, 0.2-2.0wt%, 0.2-1.8wt%, 0.2-1.5wt%, 0.2-1.2wt%, 0.2-1.0wt%, 0.5-2.0wt%, 0.5-1.8wt%, 0.5-1.5wt% or 0.5-1.2wt% of a silane-based compound relative to the total composition, for example, it may contain 0.5-1.0wt%, but is not limited thereto.

[0022] In the present invention, the diol-based compound may be propylene glycol, but is not limited thereto.

[0023] In the present invention, the silane compound may be an ethoxysilane compound, and preferably, may be one or more selected from the group consisting of fluoroethoxysilane and aminoethoxysilane, for example, fluoroethoxysilane, but not limited thereto.

[0024] Another aspect of the present invention is a deicing or anti-icing method including an applying step of applying a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound to a surface of a target object.

[0025] In the present invention, the composition may include 50.0-90.0 wt % of the diol-based compound and 0.1-2.0 wt % of the silane-based compound relative to the entire composition.

[0026] Preferably, the composition may contain 50-85wt%, 50-80wt%, 50-75wt%, 50-70wt%, 55-90wt%, 55-85wt%, 55-80wt%, 55-75wt%, 55-70wt%, 60-90wt%, 60-85wt%, 60-80wt%, 60-75wt%, 60-70wt%, 65-90wt%, 65-85wt%, 65-80wt% or 65-75wt% of the diol-based compound relative to the total composition, for example, it may contain 65-70wt%, but is not limited thereto.

[0027] Preferably, the composition may contain 0.1-1.8wt%, 0.1-1.5wt%, 0.1-1.2wt%, 0.1-1.0wt%, 0.2-2.0wt%, 0.2-1.8wt%, 0.2-1.5wt%, 0.2-1.2wt%, 0.2-1.0wt%, 0.5-2.0wt%, 0.5-1.8wt%, 0.5-1.5wt% or 0.5-1.2wt% of a silane-based compound relative to the total composition, for example, it may contain 0.5-1.0wt%, but is not limited thereto.

[0028] In the present invention, the diol-based compound may be propylene glycol, but is not limited thereto.

[0029] In the present invention, the silane compound may be an ethoxysilane compound, and preferably, may be one or more selected from the group consisting of fluoroethoxysilane and aminoethoxysilane, for example, fluoroethoxysilane, but not limited thereto.

[0030] In the present invention, the target object may be one or more metal materials selected from the group consisting of carbon steel, copper, aluminum, tungsten, and iron. For example, the target object may be carbon steel, but is not limited thereto. Effects of the Invention

[0031] The present invention relates to a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound, and a deicing or anti-icing method using the same. Since the composition has an excellent effect of delaying snow adhesion and ice formation when applied to the surface of a target object (metal material), it can be effectively used for deicing or anti-icing the surface of railway vehicles. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1The graph shows the deicing or anti-icing effect of a deicing or anti-icing composition containing a water repellent prepared according to an embodiment of the present invention.

[0033] Figure 2 This graph shows the secondary contact angles measured for a deicing or anti-icing composition containing a silane-based water repellent agent prepared according to one embodiment of the present invention. DETAILED DESCRIPTION

[0034] The present invention relates to a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound, and a deicing or anti-icing method comprising applying the deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound to the surface of a target object. Specific embodiments

[0035] Hereinafter, the present invention will be described in more detail by way of the following examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited to these examples.

[0036] Throughout the specification, unless otherwise specified, "%" used to express the concentration of a specific substance is (weight / weight)% in the case of solid / solid, (weight / volume)% in the case of solid / liquid, and (volume / volume)% in the case of liquid / liquid.

[0037] Example 1: Preparation of Deicing or Anti-icing Composition

[0038] As a basic research for developing chemical de-icing / anti-icing fluids capable of effective de-icing / anti-icing, a de-icing or anti-icing composition based on propylene glycol (PG) containing a hydrophobic component was prepared.

[0039] The propylene glycol reagent used in the experiment was purchased from Junsei Chemical Co., Ltd. (Japan). A 70 wt% aqueous solution of propylene glycol (-67.7°C) was prepared and used. Distilled water with a conductivity of 10 μS / cm or less was used as the solvent. As shown in Table 1 below, various water repellents were purchased.

[0040] Table 1: Types of water repellents

[0041] Table 2: Sample name and composition of PG-based deicing fluid

[0042] As shown in Table 2 above, deicing or anti-icing compositions were prepared by adding a hydrophobic agent at respective amounts of 0 wt %, 0.5 wt %, 1.0 wt %, 1.5 wt %, and 2.0 wt % to a propylene glycol aqueous solution. The compositions were then compared and evaluated for ice melting performance, contact angle, and anti-icing performance.

[0043] Example 2: Kinematic viscosity evaluation

[0044] The kinematic viscosity of the selected evaluation materials correlates to their sprayability through the spray system. To evaluate the viscosity properties of the prepared de-icing / anti-icing fluids, a test was conducted according to the international kinematic viscosity standard ASTM D455-06.

[0045] Specifically, a kinematic viscosity tube is cleaned with acetone and dried. A prescribed amount of sample is then placed in an oil bath at the test temperature for 20 minutes, allowing the test liquid to reach equilibrium with the temperature of the test solution. After 20 minutes, pressure is used to position the test liquid at the starting point. The time it takes to move from the starting point to the end point is measured to calculate the kinematic viscosity. Each evaluation substance is evaluated at least three times, and the average value is calculated and recorded to the second decimal place.

[0046] Table 3: Kinematic Viscosity of PG-Based Deicing Fluids

[0047] As shown in Table 3, when up to 2 wt% of the four water repellents selected for the development of de-icing / anti-icing fluids for high-speed rail vehicles were added to a propylene glycol aqueous solution, the viscosity characteristics of the solutions were analyzed. The results showed that the kinematic viscosity of the solutions ranged from 2.72 to 2.99 cSt, which was not significantly different from that of a 70 wt% pure propylene glycol solution.

[0048] It was confirmed that the viscosity characteristics of de-icing / anti-icing fluids are determined by the properties of propylene glycol (68-70 wt% of the base).Through this study, it was determined that de-icing / anti-icing fluids based on propylene glycol containing hydrophobic components can also be suitable for spray systems.

[0049] Example 3: Ice melting performance evaluation

[0050] The ice-melting capacity of the selected evaluation substances was evaluated according to the Korean Ministry of Environment's published environmental label certification standard EL610 and snow removal agent EM502-3 (2015). The test method is to generate uniform ice with a thickness of 5mm in a test container with a diameter of 23.0cm and a depth of 2.0cm. 3.2ml of the evaluation substance is sprayed on the ice and left at a test temperature of -20℃ for 30 minutes. The volume of the ice-melting liquid is then measured. A low-temperature thermostatic bath is used to maintain the test temperature. During the test, each evaluation substance is evaluated more than three times and the average value is calculated. The weight of the ice-melting liquid is measured by collecting it with a syringe and then measuring it to the fourth decimal place.

[0051] Table 4: Ice Melting Capacity of PG-Based Deicing Fluid

[0052] To develop de-icing / anti-icing fluids for high-speed rail vehicles, the amount of ice melted, a characteristic of the de-icing fluid, was evaluated. Furthermore, the amount of ice melted under the same conditions was evaluated for the type and content of the selected water repellent.

[0053] As shown in Table 4, the results show that the ice melting amount is independent of the type of hydrophobic agent, but depends on the content of propylene glycol, and as the content of the hydrophobic agent increases, the content of propylene glycol decreases, and thus the ice melting amount decreases.

[0054] The de-icing / anti-icing fluid based on propylene glycol containing a hydrophobic component melted almost the same amount of ice as a pure propylene glycol aqueous solution without the addition of a hydrophobic agent, confirming its effective performance as a de-icing fluid.

[0055] Example 4: Anti-icing performance evaluation

[0056] The anti-icing performance of the selected evaluation materials was evaluated using the water spray durability test (WSET) evaluation method for evaluating anti-icing performance against snowfall in the aircraft airframe certification standard AS5901 "SAE AMS1424 SAE AMS1428 Aircraft Anti-icing Fluid Water Spray and High Humidity Durability Test Method".

[0057] Because WSET evaluation is not available in Korea, the WSET test method used in this study modified the AS5901 conditions to those suitable for high-speed rail. The evaluation conditions are summarized in Table 5.

[0058] Table 5: WEST evaluation criteria

[0059] The evaluation method is as follows: under freezing conditions, 5 g of the composition is applied to a test piece (steel plate, high-speed rail lower part material) of 10 (W) × 30 (L) cm, and water is continuously sprayed through a nozzle for 2 hours. The sprayed water adheres to the applied test plate and is frozen on the surface of the test piece under freezing conditions (low temperature environment room maintained at -10°C to -5°C). The anti-icing performance is evaluated by the time it takes for ice to appear on the test piece.

[0060] This evaluation assumes that when de-icing / anti-icing fluid is applied to a test piece with an inclination of at least 80°, the majority of the fluid will flow downward along the inclination, and the added water repellent component will remain on the test piece surface, preventing ice from forming. Each evaluation material is evaluated at least three times, measuring the time it takes for ice to form on the test piece and the time it takes for ice to form on the entire test piece.

[0061] Anti-icing performance was evaluated using 3.3 Contact Angle Evaluation, comparing test pieces coated with a propylene glycol-based de-icing / anti-icing fluid with a high contact angle and containing 1 wt% of a DOW hydrophobic agent, test pieces coated with a propylene glycol-based de-icing / anti-icing fluid that did not contain a hydrophobic component, and test pieces not coated with de-icing / anti-icing fluid.

[0062] like Figure 1 As shown in the evaluation results, for both the test pieces without deicing / anti-icing fluid and the test pieces with deicing / anti-icing fluid that does not contain a hydrophobic component, ice formed on the test pieces starting after 10 minutes, and after 20 minutes, ice had formed on the entire test piece. The test pieces with deicing / anti-icing fluid that does not contain a hydrophobic component would have expected similar results when deicing / anti-icing fluid was applied, as most of the fluid would have flowed down the inclined surface.

[0063] For both de-icing / anti-icing fluids based on propylene glycol and containing 1 wt% of an ethoxysilane water repellent, ice formation was confirmed starting after 20 minutes, and no ice had formed on the entire test piece even after the final two hours. Contact angle evaluations indicate that the ethoxysilane water repellent rapidly formed a water repellent layer on the test piece surface, preventing snow adhesion and ice formation.

[0064] The ultimate goal of the present inventors is to develop a deicing / anti-icing fluid for high-speed rail vehicles that has the characteristics of both a deicing fluid and an anti-icing fluid. As for the deicing / anti-icing fluid based on propylene glycol containing a hydrophobic component, by spraying it in advance before railway operation and allowing the hydrophobic component to quickly form a hydrophobic layer on the bogie surface, snow adhesion and ice formation are delayed. This is expected to further improve the deicing efficiency of ice that occurs after operation.

[0065] Example 5: Contact Angle Evaluation

[0066] The contact angle of the selected evaluation materials was evaluated based on the water repellency test item 7.7 of the evaluation items of KS M 2163, a car water repellent cleaning fluid, in the Korean Industrial Standard (KS) certification standard.

[0067] Specifically, the evaluation liquid was applied to a 5 cm x 5 cm test piece (steel plate, high-speed rail lower part material) and left at room temperature for 10 minutes. Water was then dropped onto the test piece, and the contact angle based on the surface tension of the liquid (generated at the interface between the liquid and the solid surface) was measured.

[0068] In high-speed rail, due to its high speed of 300 km / h, it is expected that the sprayed de-icing / anti-icing fluid will almost disappear from the bogie surface. Therefore, in this evaluation, the above-mentioned procedure was used for the first contact angle measurement, followed by a second contact angle measurement after wiping the surface with a cloth. For each evaluation substance, the contact angles were measured at three random locations and averaged to the first decimal place.

[0069] Table 6: Contact angles of PG-based deicing fluids

[0070] As shown in Table 6, the contact angles of deicing / anti-icing fluids (four types of water repellents selected for the development of deicing / anti-icing fluids for high-speed rail vehicles, added at 0.5 wt%, 1 wt%, 1.5 wt%, and 2.0 wt% to a propylene glycol aqueous solution) were evaluated. The results indicate that higher contact angles indicate superior water repellency, and high water repellency can prevent snow from adhering and freezing in winter.

[0071] The contact angle of water on the test piece uncoated with de-icing / anti-icing fluid was measured to be 25.6°. Furthermore, the first contact angle measurement of four de-icing / anti-icing fluids containing a hydrophobic component at varying concentrations revealed a low contact angle of approximately 15.4°. These results were similar to the contact angle of a propylene glycol aqueous solution containing no hydrophobic component. This is believed to be because the hydrophilic propylene glycol aqueous solution, serving as the base, covers the entire surface of the test piece, resulting in a low contact angle due to the effect of the propylene glycol, rather than the added hydrophobic agent.

[0072] However, in the case of high-speed rail, since propylene glycol disappears during high-speed travel, it is necessary to evaluate the environmental impact that may occur during actual vehicle travel, and thus the second contact angle was also measured.

[0073] A second contact angle measurement revealed that de-icing / anti-icing fluids containing varying amounts of GCC's HEXAFOR 6380P and HYDROSIN NF-01 water repellent exhibited contact angles similar to those of uncoated test pieces, ranging from approximately 25.4 to 25.6°. However, DOW's OFS-6011 exhibited a maximum contact angle of approximately 92.5°, while DOW's Q3-9030 water repellent exhibited a high maximum contact angle of approximately 103.4°. Both GCC water repellents (non-silane compounds) failed to form a water-repellent layer on the test piece surface within a short period of time and could be easily removed with propylene glycol.

[0074] like Figure 2As shown, the two ethoxysilane-type water repellents from Dow Chemical react with water within the molecule, adhering to the test piece surface in a short period of time to form a water repellent layer, thereby exhibiting high water repellency. The fluorine-containing Q3-9030 water repellent exhibits a higher contact angle, presumably due to the low surface energy -CF3 structure within the molecule.

[0075] When the contact angles of two DOW hydrophobic agents were measured at varying concentrations, no significant change in contact angle was observed starting at 1 wt%. When evaluating the contact angles of de-icing / anti-icing fluids based on propylene glycol, a hydrophobic component, ethoxysilane-based hydrophobic agents were found to be suitable. As shown in Example 3, ice-melting performance tends to decline with increasing hydrophobic agent content and decreasing propylene glycol content, leading to the conclusion that a usage concentration of 1 wt% or less is most suitable. Industrial Applicability

[0076] The present invention relates to a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound and a deicing or anti-icing method using the same. More particularly, the present invention relates to a deicing or anti-icing technology using a composition to which 0.5-1.0 wt% of an ethoxysilane-based compound based on propylene glycol (PG) is added.

Claims

A deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound.

2. The deicing or anti-icing composition according to claim 1, characterized in that The composition includes 50.0-90.0 wt% of a diol-based compound and 0.1-2.0 wt% of a silane-based compound relative to the entire composition.

3. The deicing or anti-icing composition according to claim 1, characterized in that The glycol-based compound is propylene glycol.

4. The deicing or anti-icing composition according to claim 1, wherein The silane compound is at least one selected from the group consisting of fluoroethoxysilane and aminoethoxysilane.

5. A deicing or anti-icing method comprising the step of applying a deicing or anti-icing composition comprising a glycol-based compound and a silane-based compound to a surface of a target object.

6. The deicing or anti-icing method according to claim 5, characterized in that: The composition includes 50.0-90.0 wt% of a diol-based compound and 0.1-2.0 wt% of a silane-based compound relative to the entire composition.

7. The deicing or anti-icing method according to claim 5, characterized in that: The glycol-based compound is propylene glycol.

8. The deicing or anti-icing method according to claim 5, characterized in that: The silane compound is at least one selected from the group consisting of fluoroethoxysilane and aminoethoxysilane.

9. The deicing or anti-icing method according to claim 5, characterized in that: The target object is one or more metal materials selected from the group consisting of carbon steel, copper, aluminum, tungsten, and iron.

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