A zirconium tube rolling oil composition and a method for preparing the same

Abstract

The application discloses a zirconium pipe rolling oil composition and a preparation method thereof, and relates to the technical field of lubricating oil for metal processing. The zirconium pipe rolling oil composition is prepared from the following raw materials in parts by weight: 30-70 parts of vegetable oil, 15-40 parts of synthetic ester, 2-10 parts of extreme pressure anti-wear agent, 5-10 parts of synthetic oleic acid soap, 1-5 parts of alkali, 5-10 parts of surfactant and 0.5-2 parts of antirust agent. The zirconium pipe rolling oil composition has high lubricity, heat dissipation and washability, can meet the requirements of high-difficulty processing rolling, is easy to wash, can be completely biodegraded and is easy to handle wastewater in the later period.

Description

Technical Field

[0001] This invention relates to the field of lubricating oils for metal processing, and particularly to a zirconium tube rolling oil composition and its preparation method. Background Technology

[0002] Zirconium alloys possess excellent mechanical and nuclear properties, making them widely used in nuclear power, military, and other fields. Zirconium tubes are primarily used as cladding tubes and pressure tubes for nuclear fuel. The safety of nuclear power plants and military equipment is paramount, thus requiring extremely high performance from zirconium tubes. Zirconium tube rolling oil is an indispensable component in the production process. It is commonly used in various types of zirconium tubes for diameter expansion or cold rolling processes, such as diameter reduction and stretching. During production, the rolling oil plays a crucial role in lubrication, extreme pressure resistance, friction reduction, rust prevention, and cooling, making it a vital part of the manufacturing process.

[0003] In existing technologies, zirconium tube rolling oils mostly use low-viscosity mineral oils as base oils or water-based rolling fluids. However, for complex machining processes, existing zirconium tube rolling oils cannot meet the lubrication requirements, resulting in high surface roughness and low workpiece precision. Furthermore, mineral oil-based zirconium tube rolling oils are not easily biodegradable, making them environmentally unfriendly.

[0004] On the other hand, to meet lubrication requirements, commercially available zirconium tube rolling fluids often contain high levels of sulfur-based additives, which remain on the zirconium tube surface after processing, affecting subsequent processing steps. For example, removing oxide scale and residual lubricating oil from the zirconium tube surface requires pickling.

[0005] It is evident that existing technologies still need improvement and enhancement. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this invention is to provide a zirconium tube rolling oil composition and its preparation method, aiming to solve the technical problems of insufficient performance and difficulty in biodegradation of zirconium tube rolling oil in the prior art.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] The first aspect of the present invention provides a zirconium tube rolling oil composition, which, by weight, comprises the following raw materials: 30-70 parts of vegetable oil, 15-40 parts of synthetic ester, 2-10 parts of extreme pressure anti-wear agent, 5-10 parts of synthetic oleic acid soap, 1-5 parts of alkali, 5-10 parts of surfactant, and 0.5-2 parts of rust inhibitor.

[0009] The zirconium tube rolling oil composition, wherein the synthetic oleic soap comprises at least one of triethanolamine oleic soap, isomeric alcohol oleic soap, potassium fatty acid soap, diethanolamide coconut oil soap, and isomeric alcohol oleic soap derivatives.

[0010] The zirconium tube rolling oil composition, wherein the carbon chain length of the isomeric alcohol in the isomeric alcohol oleic acid soap or isomeric alcohol oleic acid soap derivative is 6-8.

[0011] The zirconium tube rolling oil composition, wherein the synthetic ester comprises at least one selected from saturated polyol ester, isooctyl stearate, neopentyl glycol ester, and trimethylolpropane ester.

[0012] The zirconium tube rolling oil composition, wherein the extreme pressure anti-wear agent is a phosphorus-based extreme pressure anti-wear agent.

[0013] The zirconium tube rolling oil composition, wherein the surfactant comprises at least one of alkylphenol polyoxyethylene ether, Span 80, and polyethylene glycol.

[0014] The zirconium tube rolling oil composition, wherein the rust inhibitor comprises at least one of phenyl alcohol ether phosphate, benzotriazole derivative, barium petroleum sulfonate, and tribasic acid.

[0015] The zirconium tube rolling oil composition, wherein the alkali includes at least one selected from ethanolamine, triethanolamine, dicyclohexylamine, and isopropanolamine.

[0016] The zirconium tube rolling oil composition has a kinematic viscosity of 20-50 mm at 40°C. 2 / s.

[0017] A second aspect of the present invention provides a method for preparing rolling oil, for preparing the zirconium tube rolling oil composition as described above, comprising the following steps:

[0018] Mix the base oil, synthetic ester, and rust inhibitor, and stir.

[0019] Add extreme pressure anti-wear agent and synthetic oleic acid soap, and stir;

[0020] An alkali and a surfactant are added and stirred to obtain the zirconium tube rolling oil composition.

[0021] Beneficial effects:

[0022] The first aspect of this invention provides a zirconium tube rolling oil composition that can meet the lubrication requirements of high-difficulty machining, ensuring that the zirconium tube surface is free of scratches after machining. The zirconium tube rolling oil composition also has good heat dissipation, is less prone to sticking to the mold, and does not contain sulfur-containing additives, resulting in fewer harmful element residues on the workpiece surface, which is beneficial for subsequent pickling, annealing, and other processes. The zirconium tube rolling oil composition provided by this invention is easy to clean, leaving little residual oil on the workpiece surface after pressurized rinsing, and the generated wastewater is easily treated, biodegradable, and meets environmental protection requirements.

[0023] The second aspect of the present invention provides a method for preparing rolling oil, wherein the preparation method is simple, the quality is controllable, and a large quantity of the zirconium tube rolling oil composition described above can be produced quickly. Attached Figure Description

[0024] Figure 1 The graph shows the friction coefficient test results of the zirconium tube rolling oil compositions used in the examples and comparative examples. Detailed Implementation

[0025] This invention provides a zirconium tube rolling oil composition and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0026] The first aspect of this invention provides a zirconium tube rolling oil composition, which, by weight, comprises: 30-70 parts vegetable oil, 15-40 parts synthetic ester, 2-10 parts extreme pressure anti-wear agent, 5-10 parts synthetic oleic acid soap, 1-5 parts alkali, 5-10 parts surfactant, and 0.5-2 parts rust inhibitor. The zirconium tube rolling oil composition provided by this disclosure has high lubricity, good heat dissipation, and extreme pressure anti-wear properties, meeting the requirements of high-difficulty processing. Workpieces are not easily stuck together and are easy to clean. The waste liquid after cleaning is completely biodegradable and easy to treat later.

[0027] Vegetable oils constitute the largest portion of the formulation and play a crucial role in the overall lubrication of the system, often determining the strength of the oil film formed. Simultaneously, vegetable oils determine the biodegradability of the formulation. Vegetable oils and synthetic esters contain stronger polar groups, resulting in better lubrication. Furthermore, compared to mineral oils, they exhibit better biodegradability and are more environmentally friendly.

[0028] Specifically, the vegetable oil can be low-viscosity palm oil, coconut oil, oxidized rapeseed oil, etc.

[0029] Preferably, the synthetic ester includes at least one of saturated polyol esters, isooctyl stearate, trimethylolpropane ester, 2-ethylhexyl acetate, and neopentyl glycol esters (such as neopentyl glycol dioleate).

[0030] Preferably, the kinematic viscosity of the vegetable oil and synthetic ester compounded at 40°C is 10–30 mm. 2 At / s, it has good lubrication and heat dissipation properties.

[0031] Preferably, the synthetic oleic acid soap includes at least one of triethanolamine oleic acid soap, isomeric alcohol oleic acid soap, potassium fatty acid soap, diethanolamide coconut oil soap, and isomeric alcohol oleic acid soap derivatives. These synthetic oleic acid soaps can improve the lubricity and emulsifability of the rolling oil composition system and are easy to clean and remove after processing.

[0032] Preferably, in the isomeric alcohol oleic acid soap or its derivatives, the carbon chain length of the isomeric alcohol is 6-8. The isomeric alcohol oleic acid soap provided in this disclosure can be synthesized from isomeric alcohols with a carbon chain length of 6-8 and oleic acid; the carbon chain length of the isomeric alcohol oleic acid soap can be 7, 8, 9, etc. The oleic acid soap obtained by limiting the carbon chain length exhibits both good lubricity and excellent cleaning properties in the formulation system of this disclosure, achieving an optimal balance between the two.

[0033] Preferably, the synthetic oleic acid soap has an HLB value of 5.5 to 13.5. By limiting the HLB value, the system becomes stable, easily emulsified, and requires a small amount of surfactant.

[0034] Preferably, the extreme pressure anti-wear agent is a phosphorus-based extreme pressure anti-wear agent. The phosphorus-based extreme pressure anti-wear agent includes at least one selected from phosphate esters, phosphites, and ammonium phosphate salts.

[0035] Extreme pressure (AP) anti-wear agents form a stronger oil film under harsh processing conditions to prevent contact between workpieces and reduce surface roughness. The AP anti-wear agent disclosed herein imparts excellent AP anti-wear properties to zirconium tube rolling oil compositions, providing AP lubrication effectiveness under harsh processing conditions. Compared to sulfur-containing additives, phosphorus-based additives are more biodegradable and environmentally friendly.

[0036] Preferably, the extreme pressure anti-wear agent is obtained by compounding multiple phosphorus-based extreme pressure anti-wear agents. Specifically, in the extreme pressure anti-wear agent, the mass ratio of oil-based phosphorus-based extreme pressure anti-wear agent to water-based phosphorus-based extreme pressure anti-wear agent is 1:(2-3).

[0037] After rolling, other processes are required, such as removing oxide scale and residual lubricating oil from the zirconium tube surface, which necessitates pickling. With increasing demands on workpiece processing, the zirconium tube surface is treated, for example, by adding coatings to improve oxidation resistance. All these processes require a residue-free zirconium tube surface. Surface residue can be reduced by using specific proportions and types of phosphorus-based extreme pressure agents.

[0038] Preferably, the surfactant includes at least one of alkylphenol polyoxyethylene ether, Span 80, and polyethylene glycol. More preferably, the alkylphenol polyoxyethylene ether can be nonylphenol polyoxyethylene ether. The polyethylene glycol can be PEG400Mo, PEG400DO, PEG600Mo, PEG600DO, etc.

[0039] Preferably, the rust inhibitor includes at least one of phenyl alcohol ether phosphate, benzotriazole derivative, barium petroleum sulfonate, and tribasic acid.

[0040] Preferably, the base includes at least one selected from ethanolamine, triethanolamine, dicyclohexylamine, and isopropanolamine.

[0041] Preferably, the kinematic viscosity of the zirconium tube rolling oil composition at 40°C is 20–50 mm. 2 / s.

[0042] The zirconium tube rolling oil composition provided by this invention can be applied to the production of zirconium tubes of various diameters, playing a lubricating role, meeting the requirements of high-difficulty processing procedures such as multi-process zirconium tube expansion and contraction, effectively protecting the expansion head, improving the surface brightness of zirconium tube workpieces and reducing surface roughness, and extending the workpiece accuracy and tool life.

[0043] A second aspect of the present invention provides a method for preparing rolling oil, for preparing the zirconium tube rolling oil composition described above, comprising the following steps:

[0044] Mix the base oil, synthetic ester, and rust inhibitor, and stir.

[0045] Add extreme pressure anti-wear agent and synthetic oleic acid soap, and stir;

[0046] Add alkali and surfactant, stir, and obtain the zirconium tube rolling oil composition.

[0047] Preferably, the temperature is controlled at 50-60℃ during the stirring process in each of the above steps.

[0048] Example 1

[0049] A zirconium tube rolling oil composition, by weight, comprises the following raw materials: 50 parts vegetable oil, 23.8 parts synthetic ester, 5 parts extreme pressure anti-wear agent, 8 parts synthetic oleic acid soap, 4 parts alkali, 8 parts surfactant, and 1.2 parts rust inhibitor.

[0050] The vegetable oil is low-viscosity palm oil;

[0051] The synthesized ester is isooctyl stearate;

[0052] The extreme pressure anti-wear agent is a mixture of oil-soluble phosphate ester and water-soluble phosphate ester in a mass ratio of 1:2;

[0053] The synthetic oleic acid soap is triethanolamine oleic acid soap;

[0054] The alkali is triethanolamine;

[0055] The surfactant is nonylphenol polyoxyethylene ether;

[0056] The rust inhibitor is barium petroleum sulfonate;

[0057] The method for preparing the zirconium tube rolling oil composition includes the following steps:

[0058] S001. Mix the vegetable oil, synthetic ester and rust inhibitor, and stir at a constant speed at a temperature of 50℃~60℃;

[0059] S002. Add extreme pressure anti-wear agent and synthetic oleic acid soap, and stir at a constant speed while maintaining a temperature of 50℃~60℃;

[0060] S003. Add alkali and surfactant, maintain the temperature at 50℃~60℃ and stir at a uniform speed, then cool down to 40℃ and stop stirring to obtain the zirconium tube rolling oil composition.

[0061] Example 2

[0062] A zirconium tube rolling oil composition, by weight, comprises the following raw materials: 40 parts vegetable oil, 34.2 parts synthetic ester, 6 parts extreme pressure anti-wear agent, 9 parts synthetic oleic acid soap, 5 parts alkali, 5 parts surfactant, and 0.8 parts rust inhibitor.

[0063] The vegetable oil is a mixture of palm oil and coconut oil in a mass ratio of 3:1;

[0064] The synthesized ester is trimethylolpropane ester;

[0065] The extreme pressure anti-wear agent is a mixture of oil-soluble phosphate ester and water-soluble phosphate ester in a mass ratio of 1:2.5;

[0066] The synthetic oleic acid soap is a diethanolamide coconut oil acid soap;

[0067] The alkali is a mixture of ethanolamine and triethanolamine in a mass ratio of 1:2;

[0068] The surfactant is Span 80;

[0069] The rust inhibitor is phenyl alcohol ether phosphate;

[0070] The preparation method of the zirconium tube rolling oil composition is the same as in Example 1.

[0071] Example 3

[0072] A zirconium tube rolling oil composition, by weight, comprises the following raw materials: 60 parts vegetable oil, 17.3 parts synthetic ester, 8 parts extreme pressure anti-wear agent, 4 parts synthetic oleic acid soap, 6 parts alkali, 4 parts surfactant, and 0.7 parts rust inhibitor.

[0073] The vegetable oil is a mixture of rapeseed oil and coconut oil in a mass ratio of 4:1.

[0074] The synthesized ester is neopentyl dioleate;

[0075] The extreme pressure anti-wear agent is a mixture of oil-soluble phosphate ester and water-soluble phosphate ester in a mass ratio of 1:3;

[0076] The synthetic oleic acid soap is triethanolamine oleic acid soap;

[0077] The alkali is a mixture of ethanolamine and isopropanolamine in a mass ratio of 4:1;

[0078] The surfactant is PEG400Mo;

[0079] The rust inhibitor is a benzotriazole derivative;

[0080] The preparation method of the zirconium tube rolling oil composition is the same as in Example 1.

[0081] Example 4

[0082] A zirconium tube rolling oil composition, which differs from Example 1 in that the extreme pressure anti-wear agent is a phosphite.

[0083] Example 5

[0084] A zirconium tube rolling oil composition, which differs from Example 1 in that the extreme pressure anti-wear agent is a fatty alcohol phosphate ester.

[0085] Comparative Example 1

[0086] A zirconium tube rolling oil composition, which differs from Example 1 in that it uses 10# white oil instead of vegetable oil.

[0087] Comparative Example 2

[0088] A zirconium tube rolling oil composition, which differs from Example 1 in that the extreme pressure anti-wear agent is a mixture of oil-soluble phosphate ester and water-soluble phosphate ester in a mass ratio of 2:1.

[0089] Comparative Example 3

[0090] This comparative example is a commercially available water-based zirconium tube rolling oil with mineral oil as the base oil.

[0091] Comparative Example 4

[0092] This comparative example is a commercially available pure zirconium tube rolling oil based on mineral oil.

[0093] Comparative Example 5

[0094] A zirconium tube rolling oil composition, which differs from Example 1 in that the vegetable oil comprises 8 parts and the synthetic ester comprises 10 parts.

[0095] Comparative Example 6

[0096] A zirconium tube rolling oil composition, which differs from Example 1 in that the vegetable oil comprises 20 parts and the synthetic ester comprises 70 parts.

[0097] The properties of the zirconium tube rolling oil in the above embodiments and comparative examples were tested.

[0098] The kinematic viscosity test was conducted in accordance with GB / T 265-1988, "Determination of Kinematic Viscosity and Calculation of Dynamic Viscosity of Petroleum Products".

[0099] The test method for cleanability is as follows: Take a 10cm×5cm zirconium alloy plate and weigh it as m1. Apply 2g of sample to the zirconium plate and rinse it with a pressure nozzle for 20s. After rinsing, dry it and weigh the steel plate as m2. Calculate the mass difference Δm between m2 and m1. A mass difference of less than 0.02g is defined as excellent cleanability, a mass difference between 0.02g and 0.05g is defined as medium cleanability, and a mass difference of more than 0.05g is defined as poor cleanability.

[0100] The lubrication performance test was conducted in accordance with GB / T 12583-1998, "Determination of Extreme Pressure Properties of Lubricants".

[0101] The friction and wear performance test was conducted in accordance with the "NB / SH / T 0847-2010 Determination of Friction and Wear Performance of Extreme Pressure Lubricating Oil - SRV Test Machine Method".

[0102] Extreme pressure performance testing was conducted in accordance with GB / T 11144-2007 "Determination of Extreme Pressure Performance of Lubricating Fluids - Timken Method".

[0103] The temperature difference was determined using the Timken test method, with a uniform and fixed temperature change before and after a 10kg load.

[0104] The wear volume and surface roughness were measured using a white light interferometer.

[0105] The stability test method is as follows: heat at 100 degrees Celsius for 6 hours, and observe the layering after returning to room temperature. No layering indicates excellent stability, slight turbidity indicates medium stability, and severe layering and turbidity indicate poor stability.

[0106] The corresponding test results are as follows:

[0107] Table 1

[0108]

[0109] Table 2

[0110]

[0111]

[0112] As shown in Tables 1 and 2, the zirconium tube rolling oil compositions provided in Examples 1-5 exhibit excellent lubrication and heat dissipation properties, are easy to clean, and have good stability. During testing, the zirconium tube rolling oil compositions showed small temperature rise, low coefficient of friction, small wear volume, low surface roughness, and high Timken test load. Further combined with… Figure 1 The test results show that the zirconium tube rolling oil composition provided by this invention has a low coefficient of friction, which meets the requirements for use.

[0113] As can be seen from the comparison between Example 1 and Comparative Example 1, after replacing vegetable oil with mineral oil, the lubricity of the resulting zirconium tube rolling oil composition is significantly worse, the wear marks and wear volume are larger, and the temperature rise is greater.

[0114] The ratio of oil-soluble phosphate ester to water-soluble phosphate ester in Comparative Example 2 is greater than the scope of protection of this invention. According to the test results, the stability of the rolling oil composition obtained in Comparative Example 2 is worse.

[0115] Comparative Example 3 is a water-based zirconium tube rolling oil with mineral oil as the base oil. The test results show that its cleaning properties, lubricity, wear volume, surface roughness, and temperature rise are all inferior to those of Examples 1-5.

[0116] Comparative Example 4 is a pure oil-based zirconium tube rolling oil with mineral oil as the base oil. The test results show that its cleaning properties, lubricity, wear volume, surface roughness, and temperature rise are all inferior to those of Examples 1-5.

[0117] In Comparative Examples 5 and 6, the amount of vegetable oil or synthetic ester used was not within the range of the amount claimed by this invention. From the test results, the test results of its cleaning properties, lubricity, stability, wear volume, surface roughness and temperature rise were also not as good as those of Examples 1-5.

[0118] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A zirconium tube rolling oil composition, characterized in that, The raw materials for its preparation, by weight, are: 50 parts vegetable oil, 23.8 parts synthetic ester, 5 parts extreme pressure anti-wear agent, 8 parts synthetic oleic acid soap, 4 parts alkali, 8 parts surfactant, and 1.2 parts rust inhibitor; wherein the vegetable oil is low viscosity palm oil; the synthetic ester is isooctyl stearate; the extreme pressure anti-wear agent is phosphite; the synthetic oleic acid soap is triethanolamine oleic acid soap; the alkali is triethanolamine; the surfactant is nonylphenol polyoxyethylene ether; and the rust inhibitor is barium petroleum sulfonate.

2. The zirconium tube rolling oil composition according to claim 1, characterized in that, It has a kinematic viscosity at 40°C of 35 mm 2 / s.

3. A method for preparing rolling oil, characterized in that, The method for preparing the zirconium tube rolling oil composition according to claim 1 or 2 includes the following steps: Mix the base oil, synthetic ester, and rust inhibitor, and stir. Add extreme pressure anti-wear agent and synthetic oleic acid soap, and stir; An alkali and a surfactant are added and stirred to obtain the zirconium tube rolling oil composition.

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