CN106566625B - One vegetable oil base titanium alloy emulsifies working fluid - Google Patents

One vegetable oil base titanium alloy emulsifies working fluid Download PDF

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CN106566625B
CN106566625B CN201610864193.4A CN201610864193A CN106566625B CN 106566625 B CN106566625 B CN 106566625B CN 201610864193 A CN201610864193 A CN 201610864193A CN 106566625 B CN106566625 B CN 106566625B
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working fluid
titanium alloy
emulsifies
parts
alloy according
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CN106566625A (en
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刘腾飞
戴媛静
张晨辉
雒建斌
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Chaohua Technology Foshan Co ltd
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Tsinghua University
Tianjin Institute of Advanced Equipment of Tsinghua University
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
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    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
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    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
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    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
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    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C10M2215/222—Triazines
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
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    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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    • C10M2223/04—Phosphate esters
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    • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
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    • C10M2229/02—Unspecified siloxanes; Silicones
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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Abstract

The invention provides a kind of titanium alloy emulsification working fluid, by weight, comprising: and 20-60 parts of base oil, 3-30 parts of emulsifier, 3-20 parts of corrosion inhibitor, agent 5-30 parts of base number deposit, 0-20 parts of other auxiliary agents, water.The working fluid greasy property that the invention provides is good, stability is high, rustless property is prominent, hard water is adaptable, friendly to operator and ecological environment security.

Description

One vegetable oil base titanium alloy emulsifies working fluid
Technical field
The invention belongs to intermetallic composite coating auxiliary agent technical fields, specifically, being a kind of plant suitable for aero titanium alloy Oil base emulsifies working fluid.
Background technique
Titanium alloy has many advantages, such as that specific strength is high, heat resistance is good, corrosion-resistant, resourceful, has extensively in Aeronautics and Astronautics field General application, and the industrial departments such as shipbuilding, metallurgy, chemical industry, light industry, medical treatment are gradually expanded to, have the potentiality that grow a lot；However, Titanic alloy machining is poor, belongs to difficult-to-machine material, specific manifestation are as follows: poor thermal conductivity, plasticity are low, hardness is high, elasticity modulus is low, bullet Property deflection is big, chill phenomenon is serious.It is with respect to 25% -38% that machinability is No. 45 steel.
For the processing efficiency and precision for improving titanium alloy, generally processed under conditions of using working fluid.Commonly Working fluid is poor to titanium alloy greasy property, processing efficiency is low；In addition, traditional processing liquid is oily based on mineral oil, biodegrade Property is poor, and extended residual causes environmental pollution in water body and soil, meanwhile, the oil smoke generated in use process can be to operator Body generates harm；Sodium nitrite antirust agent, phenol fungicide and the aldehydes being added thereto to improve working fluid performance Compound etc. is toxic, and Long Term Contact will increase cancer morbidity；S contained in mineral oil, surfactant and extreme pressure agent, P, Cl etc. can make dry skin, cracking, redness, lead to skin disease.
Therefore, the environment-friendly titanium alloy emulsification working fluid for researching and developing high-lubricity has a very important significance.
Summary of the invention
The invention is to solve the problems of the prior art, provides that a kind of greasy property is good, stability is high, rust-preventing characteristic It can protrude, hard water is adaptable, emulsifies working fluid to the plant oil base titanium alloy of operator and ecological environment security close friend.
The titanium alloy that the invention provides emulsifies working fluid, by weight, comprising:
20-60 parts of base oil,
3-30 parts of emulsifier,
Base number lays in agent 5-30 parts,
0-40 parts of other auxiliary agents,
Water.
Wherein, other described auxiliary agents preferably include following one or more components:
3-20 parts of corrosion inhibitor,
0.5-5 parts of antibacterial agent,
0.2-5 parts of antioxidant,
0.2-5 parts of defoaming agent.
Wherein, the additional amount of water is so that titanium alloy emulsification working fluid is able to maintain that stable emulsion state and reaches tool Have subject to good mobile performance, those skilled in the art can be adjusted and add as needed, the additive amount of water in this case Generally in 3-15 parts by weight.
Wherein, the base oil be oxidation vegetable oil, preferably epoxide number be 3% -6% oxidation rapeseed oil.Invention human hair Existing, when epoxide number is 3% -6%, hydroxyl, ester group and the epoxy group that oxidation rapeseed oil contains mutually coordinated can be acted on, jail Admittedly being adsorbed on titanium alloy surface, continuous lubricating film is formed, the sustainable friction for reducing workpiece and cutter in cutwork improves and adds Work precision；In addition, unsaturated bond content is low in oxidation vegetable oil, oxidation resistance is strong, is conducive to extend service life.
Wherein, the emulsifier is the mixture of aliphatic acid polyethenoxy ether, alkyl polyethylene glycol acid esters, diterpene carboxylic acid, Preferred mass ratio is (5 ± 0.2): (2 ± 0.2): (1 ± 0.2).Inventors have found that the poly- second of aliphatic acid polyethenoxy ether, alkyl Diolate oleophylic based structures are similar to oxidation vegetable oil；Diterpene carboxylic acid is small molecule resin acid as a kind of and fatty acid, It can be inlaid into the gap of oil-water emulsion interfacial film, increase interfacial film strength, reduce interface energy；Composite emulsifier HLB value is 5- 7, it is also close with oxidation vegetable oil, therefore there is good emulsification to oxidation vegetable oil；Meanwhile containing various active base Group can promote absorption of the base oil to titanium alloy, enhance film strength, improve lubricity；In addition, the poly- second of the alkyl of highly branched chain Diolate is adaptable to hard water, and foam is low.
Wherein, the base number deposit agent is selected from least one of saturation hydramine, cyclohexylamine, and the saturation hydramine is exemplary Example include ethanol amine, diethanol amine, triethanolamine, N methyldiethanol amine, diglycolamine etc..Inventors have found that such Base number deposit agent can effectively adjust the pH value and total alkalinity of working fluid, and can increase stability of emulsion to a certain extent.
Further, the base number deposit agent preferably adjusts the pH value of working fluid described in this case to 8-10, described at this time It is 10-20 parts that base number, which lays in the preferred additive amount of agent,.Inventors have found that rustless property reduces if cutting fluid PH < 8.0, it is easily right Metal causes chemical attack, and is easier to breed spoilage organisms；And if PH > 10.0, easy stimulation applications person's skin, meanwhile, perishable two Property metal.
Wherein, the corrosion inhibitor is the mixture of borate, alcohol ether phosphate, methine benzotriazole, preferred matter Amount is than being (7 ± 0.2): (2 ± 0.2): (1 ± 0.2).Inventors have found that using the compound corrosion inhibitor not only to single gold Category has good corrosion inhibition, moreover it is possible to effectively slow down the galvanic corrosion between different metal.
Wherein, the antibacterial agent is Hexahydrotriazine compounds, iodopropynyl butyl carbamate, pyridine sulphur copper sodium Mixture, preferred mass ratio are (2 ± 0.2): (1 ± 0.2): (1 ± 0.2).Inventors have found that the compounding antibacterial agent can be effective Inhibit the growth of bacterium, fungi, and small to human body and environmental hazard.
Wherein, the antioxidant can be common antioxidant in metal working fluid, preferably 2,6- di-t-butyl Paracresol (T501).
Wherein, the defoaming agent can be common defoaming agent in metal working fluid, and preferably polyether-silicone is copolymerized Object.
The beneficial effects of the present invention are:
(1) safety and environmental protection: the present invention is free of mineral oil, nitrite, phenol and aldehydes additive, is free of the pole S, P, Cl Additive is pressed, it is work circumstances safe, tasteless, it is nonirritant to human skin and respiratory tract；It is degradable, it is environmentally friendly.
(2) high-lubricity: the present invention contains a large amount of oxidation rapeseed oils, and composite emulsifier of arranging in pairs or groups can be in titanium alloy surface shape At continuous oil film, Pb value and Pd value with higher can reduce cutter in the friction of surface of test piece, improve the processing of workpiece Quality；
(3) excellent antirust rust inhibition: the present invention has good antirust, corrosion inhibition, moreover it is possible to effectively slow down different gold Galvanic corrosion between category.
(4) high base number deposit: base number deposit of the present invention is high, and pH value is steady in a long-term in use process, more particularly to through controlling It maintains between 8.0-10.0, be conducive to metal rust preventing and inhibit spoilage organisms growth.
(5) high hardness adaptability: hard water adaptability of the present invention is good, can hardness 1360ppm (including 1360ppm) below Water in keep stablize, will not be demulsified failure.
(6) high stability: physico-chemical property and biological property of the present invention are stablized, and are not easy layering demulsification, are not easy putrid and deteriorated, follow Ring long service life, comprehensive cost performance are high.
(7) high cooling: the anti-bubble ability of the present invention is strong, have excellent cooling performance, can quickly, be fully cooled workpiece and Cutter.
Detailed description of the invention
Fig. 1 is the greasy property detection curve of embodiment 1 and comparative example 1-1, comparative example 1-2 to TC4 titanium alloy；
Fig. 2 is the absorption property detection curve of embodiment 1 and comparative example 1-1, comparative example 1-2 to TC4 titanium alloy；
Fig. 3 is the greasy property detection curve of embodiment 2 and comparative example 2-1, comparative example 2-2 to TC4 titanium alloy；
Fig. 4 is the absorption property detection curve of embodiment 2 and comparative example 2-1, comparative example 2-2 to TC4 titanium alloy；
Fig. 5 is the greasy property detection curve of embodiment 1 and comparative example 4 to TC4 titanium alloy；
Fig. 6 is embodiment 1 and comparative example 4 to TC4 cylinder table top grinding defect morphology.
Specific embodiment
The embodiment of the present invention is described below in detail, this is merely a preferred embodiment of the present invention, and is not used to limit The range that the present invention is implemented leads correlation although the contents of the present invention are discussed in detail by following embodiments It for the scientific worker and technical staff in domain, can still modify to each embodiment, or special to part of technology Sign is equivalently replaced.It is all described in the scope of the present invention patent within, any modification, equivalent replacement, improvement and so on, It should all be included in the protection scope of the present invention.
One, the selection of raw material:
The embodiment of the present invention selects following raw material:
Aoxidize rapeseed oil: Hangzhou the Kunlun special type lubricant Co., Ltd, C101；
Castor oil polyoxyethylene ether: Hefei Li Xin Chemical Co., Ltd., EL40；
Alkyl polyglycolic acid rouge: structural formulaCompound；
Diterpene carboxylic acid: Jinan Jin Quan Chemical Co., Ltd., R7065；
Triethanolamine borate: Shanghai De Mao Chemical Co., Ltd., 302M；
Methyl benzotriazazole: Jiangyin Yin Lin Chemical Co., Ltd., TTA；
Pyridine sulphur copper sodium: the magnificent Chemical Co., Ltd. in Zhengzhou hundred million, 714；
Iodo propinyl n-butyl carbamate: the magnificent Chemical Co., Ltd. in Zhengzhou hundred million, 502；
Hexahydrotriazine compounds: ethoxy perhydro-s-triazine；
Alcohol ether phosphate: DOW Chemical antirust agent GT-GP；
Polyethers-silane copolymer: wound Degussa defoaming agent MR-2124 is won；
Water: deionized water；
Other raw materials are shown in embodiment, comparative example composition table.
Two, preparation method:
1. base oil and oil soluble additive are added in reaction kettle, it is heated to 50-70 DEG C, stirring and dissolving is to being clarified Transparent oil A；
2. water and water-soluble additives are added in agitator, stirring is to being completely dissolved as clear liquid B；
3. B is added in A under conditions of (50-70 °) stirring of heating；
4. continuing stirring after addition uniformly to be clarified to system to get former to plant oil base titanium alloy emulsification working fluid Liquid.
Three, detection method
3.1 greasy property
Lubricity of the present invention using multifunction friction wear testing machine SRV-4 test titanium alloy cutting liquid, friction pair: YG8 alloying pellet-TC4 cylinder table top；Load: 200N；Stroke: 2mm；Frequency: 20Hz；Temperature: 25 DEG C, working fluid concentration: 5%.
3.2 absorption property
The present invention uses absorption property of the Q-Sense E4 system testing titanium alloy to working fluid, adsorption temp: 25 DEG C；Add Work liquid concentration: 5%.
3.3 galvanic corrosion inhibitions
A) different working fluids to be measured are diluted to by 5% lotion with deionized water, be placed in a beaker；
B) different metal (+7075 aluminium of cast iron) is stacked together, contact surface fills working fluid to be measured, and is soaked in beaker In；
C) it will be placed in 55 DEG C of baking ovens and place 5 days immersed with the beaker of metal, observe the corrosion condition of metal contact surface.
3.4 other performances
Other correlated performances are detected referring to respective standard.
Four, embodiment 1, comparative example 1-1 and comparative example 1-2
Using above-mentioned preparation method, embodiment 1 and comparative example 1-1, comparative example 1-2 are prepared by table 1 respectively.
1 embodiment 1 and comparative example 1-1 of table, comparative example 1-2 working fluid form
As seen from Figure 1, it selects working fluid prepared by oxidation rapeseed oil to be better than the greasy property of titanium alloy to adopt The working fluid prepared by blown castor oil, and the oxidation rapeseed oil that epoxide number is 5% will select better than epoxy the effect of lubrication The processing liquid product that value is 2%.
In terms of quality of adsorption (Fig. 2), quality of adsorption of the titanium alloy to embodiment 1 (the rapeseed oil raw material of 5% epoxide number) Much larger than comparative example 1-1 (the rapeseed oil raw material of 2% epoxide number) and comparative example 1-2 (blown castor oil raw material).
Five, embodiment 2, comparative example 2-1 and comparative example 2-2
Using above-mentioned preparation method, embodiment 2 and comparative example 2-1, comparative example 2-2 are prepared by table 2 respectively.
2 embodiment 2 and comparative example 2-1 of table, comparative example 2-2 working fluid form
As seen from Figure 3, with aliphatic acid polyethenoxy ether, alkyl polyethylene glycol acid esters, diterpene carboxylic acid according to mass ratio The embodiment 2 of 5:2:1 composite emulsifier preparation has good lubricity to titanium alloy, the comparative example 2- under other compound proportions 1 lubricity relatively uses the lubricity of other formulas emulsifier (comparative example 2-2) also to make moderate progress.
In terms of quality of adsorption (Fig. 4), titanium alloy is much larger than comparative example 2-1 and comparative example to the quality of adsorption of embodiment 2 2-2, comparative example 2-1 also have the effect centainly improved relative to comparative example 2-2 in terms of adsorptivity.
In terms of storage stability, the results are shown in Table 3, and the storage stability of embodiment 2 is best, comparative example 2-1 times It, comparative example 2-2 is worst.
The storage stability of 3 embodiment 2 and comparative example 2-1 of table, comparative example 2-2
Six, embodiment 3, comparative example 3-1 and comparative example 3-2
Using above-mentioned preparation method, embodiment 3 and comparative example 3-1, comparative example 3-2 are prepared by table 4 respectively.
4 embodiment 3 and comparative example 3-1 of table, comparative example 3-2 working fluid form
The galvanic corrosion inhibition of embodiment 3 and comparative example 3-1, comparative example 3-2 to (+7075 aluminium of cast iron) between different metal As shown in table 5.
The storage stability of 5 embodiment 3 and comparative example 3-1 of table, comparative example 3-2
Seven, embodiment 1, comparative example 4
Comparative example 4 is the high-end commercial titanium alloy emulsion cutting fluid X of certain import.
Embodiment 1 and comparative example 4 are to TC4 titanium alloy greasy property as shown in Fig. 5, Fig. 6 and table 6.It can be seen that compared to Comparative example 4, the plant oil base titanium alloy emulsification working fluid obtained according to embodiment 1 are with lower friction to TC4 titanium alloy Several and more stable COF curves, while polishing scratch is smaller, illustrates that it is good to the lubricity of titanium alloy.
6 TC4 cylinder table top polishing scratch size of table
Eight, other performance indicators
Using above-mentioned preparation method, embodiment 4, embodiment 5 are prepared by table 7 respectively.
7 embodiment 4 of table, 5 working fluids composition
According to other physical and chemical performance indexs of the embodiment obtained emulsification of plant oil base titanium alloy working fluid and comparative example 4 It is shown in Table 8.
The physical and chemical performance index of 8 embodiment and comparative example 4 of table
The foregoing is merely the preferred embodiments of the invention, are not intended to limit the invention creation, all at this Within the spirit and principle of innovation and creation, any modification, equivalent replacement, improvement and so on should be included in the invention Protection scope within.

Claims (10)

1. a kind of titanium alloy emulsifies working fluid, by weight, comprising:
20-60 parts of base oil,
3-30 parts of emulsifier,
Base number lays in agent 5-30 parts,
0-40 parts of other auxiliary agents,
3-15 parts of water；
The base oil is the oxidation rapeseed oil that epoxide number is 3% -6%；The emulsifier is aliphatic acid polyethenoxy ether, alkane The mixture of base polyethylene glycol acid esters, diterpene carboxylic acid, the aliphatic acid polyethenoxy ether, alkyl polyethylene glycol acid esters, diterpene carboxylic The mass ratio of acid is (5 ± 0.2): (2 ± 0.2): (1 ± 0.2)；
Other described auxiliary agents include following one or more components: corrosion inhibitor, antibacterial agent, antioxidant, defoaming agent.
2. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the base number deposit agent is selected from saturated alcohols At least one of amine, cyclohexylamine.
3. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the base number deposit agent is selected from ethyl alcohol At least one of amine, diethanol amine, triethanolamine, N methyldiethanol amine, diglycolamine, cyclohexylamine.
4. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the pH value of the working fluid is 8-10.
5. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that other described auxiliary agents include following one kind Or various ingredients:
3-20 parts of corrosion inhibitor,
0.5-5 parts of antibacterial agent,
0.2-5 parts of antioxidant,
0.2-5 parts of defoaming agent.
6. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the corrosion inhibitor be borate, The mixture of alcohol ether phosphate, methine benzotriazole.
7. titanium alloy according to claim 6 emulsifies working fluid, which is characterized in that the borate, alcohol ether phosphate, secondary The mass ratio of methyl benzotriazole is (7 ± 0.2): (2 ± 0.2): (1 ± 0.2).
8. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the antibacterial agent is Hexahydrotriazine chemical combination Object, iodopropynyl butyl carbamate, pyridine sulphur copper sodium mixture.
9. titanium alloy according to claim 8 emulsifies working fluid, which is characterized in that the Hexahydrotriazine compounds, iodo Propynyl butylcarbamate, pyridine sulphur copper sodium mass ratio be (2 ± 0.2): (1 ± 0.2): (1 ± 0.2).
10. titanium alloy according to claim 1 emulsifies working fluid, which is characterized in that the antioxidant is 2,6-, bis- uncle Butyl paracresol, the defoaming agent are polyether siloxane copolymers.
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