CN104877736A - Boron-free and phosphorus-free aluminum alloy piston micro-emulsification processing liquid, dilution liquid and preparation method thereof - Google Patents
Boron-free and phosphorus-free aluminum alloy piston micro-emulsification processing liquid, dilution liquid and preparation method thereof Download PDFInfo
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- CN104877736A CN104877736A CN201410070368.5A CN201410070368A CN104877736A CN 104877736 A CN104877736 A CN 104877736A CN 201410070368 A CN201410070368 A CN 201410070368A CN 104877736 A CN104877736 A CN 104877736A
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Abstract
The present invention discloses a boron-free and phosphorus-free aluminum alloy piston micro-emulsification processing liquid, a dilution liquid, a preparation method and uses thereof. The micro-emulsification processing liquid comprises, by weight, 25-32% of mineral oil, 2-5% of a nonionic surfactant, 2-4% of petroleum sodium sulfonate, 3-6% of an auxiliary emulsifier, 11-15% of amine, 1-2% of dicarboxylic acid, 4-7% of an anhydride, 5-8% of an oil additive, 0.5-1% of a preserve sterilization agent, 0.1-0.3% of an emulsification silicon oil defoamer, and the balance of water. According to the micro-emulsification processing liquid of the present invention, the use of the boron-containing additive harmful for human body and the phosphorus additive with the characteristic of no environmental protection is avoided, the micro-emulsification processing liquid does not contain chlorine and has characteristics of no harm on human body, good pH value stability, and long service life; the micro-emulsification processing liquid has excellent hard water resistance and excellent lubrication performance through the unique formula; and compared with the emulsification processing liquid in the prior art, the micro-emulsification processing liquid of the present invention has characteristics of good cooling property and improvement of processing precision of the processed part.
Description
Technical field
The present invention relates to metal working fluid field, particularly relate to a kind of without boron without phosphorus aluminium-alloy piston microemulsified working fluid, its diluent, and preparation method thereof.
Background technology
Piston for engine power, weather resistance, economy, discharge all importants. and a particular job environment of high temperature residing for piston, high pressure, high-speed motion. make it must possess very high performance requriements.At the initial stage that piston is born, use cast-iron piston, along with the progress of technology, there is the aluminium-alloy piston of low density, superior thermal conductivity, be widely used now.
Aluminium alloy is compared with cast iron materials with most of steel, has an obvious advantage, namely lower yield strength.Therefore, the cutting force needed in the aluminium alloy course of processing is lower, can suitably improve cutting speed and charge ratio.But in actual production process, the snappiness of aluminium alloy may serve problem to machining band.First easily occur bonding phenomenon, aluminium chip is easily bonded to tool surface, has a strong impact on the surfaceness of workpiece or forms built-up edge.Secondly, because aluminium alloy has high ductibility, it may form long streak flaw, and working angles can be made to become difficulty, and the chip simultaneously cut not easily is pulled away.Again, because aluminum alloy chemically activity is comparatively strong, in cutting process, easily occur that workpiece oxidation is eclipsed, produce the problems such as blackspot.
In current mechanical processing industry at home, for aluminium-alloy piston processing water-soluble working fluid mainly based on emulsion, as CN101597537A discloses a kind of aluminum alloy piston processing fluid formula and preparation method thereof, described working fluid is made up of the raw material of following weight percent: white mineral oil 45-55%, di-carboxylic acid amine rust-preventive agent 1-2%, aluminum alloy corrosion inhibitor 0.05-0.1%, petroleum sodium sulfonate 5-8%, Viscotrol C sulfanilic acid 8-12%, trolamine 4-6%, dimerization hydrochlorate 2-5, boric acid ester 10-12%, polyvalent alcohol synthetic ester 5-8%, sorbester p17 3-5%, polyoxyethylene nonylphenol ether 2-3%, long chain aliphatic alcohol 3-5%.Metal working fluid industry is well-known, and emulsion exists following Railway Project:
1, spatter property is poor.The cleanup action of emulsion is mainly by oleate soap class and anion surfactant, due to the calcium sensitization of oleate soap class in the course of processing, tensio-active agent is impelled to reduce, so that cleaning performance completely dissolve, meanwhile, the Kun such as missible oil, slag ash are dissolved in together, form greasy filth, firmly be adsorbed on the surface of guide rail, piston, frock, affect processing quality;
2, life cycle is short, apt to deteriorate smelly.Due to the oil-in-water-type that emulsion is a kind of extremely unstable, in use procedure, oil balance is usually destroyed, and the particularly effect of high temperature season microorganism, makes emulsion destroy, and sends special stench, makes operator easily suffer from tetter.
3, cooling is poor.In the course of processing, the heat of workpiece and cutter can not fast, effectively, in time processed liquid take away, the temperature of workpiece and cutter is too high, easily cause workpiece thermal distortion, affect size and the working accuracy of workpiece, cutter also can Yin Wendu too high, wearing and tearing are too fast, reduction of service life.
In addition, generally all use borate to make rust-preventive agent or make extreme pressure lubricant with boric acid ester in CN101597537A and aluminum alloy piston processing fluid conventional in the market, the third time announcement of REACH regulation is shown great attention to material (SVHC) and is comprised boric acid and compound thereof, assert that boric acid and compound thereof belong to the 2nd class reproductive system toxicant, detect and be limited to 0.01%, America and Europe etc. are national at present progressively limits the application of boron system additive in metal working fluid.
Finally, generally phosphoric acid salt and organophosphorus is all used to do aluminium inhibiter in aluminum alloy piston processing fluid conventional in the market, but it is well-known, phosphorus easily causes body eutrophication, planktonic organism and algae amount reproduction, and the oxygen level of water declines, water quality deterioration is muddy, fishes and shrimps are difficult to existence, and the contaminated algae of raised growth produces again a large amount of algae toxins, and these algae toxins are again carcinogenic substances.Present every country has limited the discharge of phosphorus all.Meanwhile, in metal working fluid, phosphorus system additive is also the nutrition source of bacterium, greatly have impact on the work-ing life of cutting fluid.
Summary of the invention
Technical problem to be solved by this invention is that overcoming the existing working fluid for aluminium-alloy piston is mainly emulsion, spatter property is poor, life cycle is short, cooling is poor, and containing the defect to human body and the disadvantageous material of environment such as boron and phosphorus, provide a kind of without boron without phosphorus aluminium-alloy piston microemulsified working fluid, diluent and preparation method.Emulsifying type working fluid of the present invention can be used for the operations such as the pin-and-hole roughing of aluminium-alloy piston, external diameter roughing, machining of oil hole, annular groove processing, external diameter precision work and pin-and-hole precision work.This working fluid is not chloride, harmless; Not phosphorous, environmental protection and not easily raw bacterium is smelly, pH stability is good, long service life; There is outstanding stability in hard water energy and lubricity; Compared with emulsification working fluid, cooling is better, can improve the working accuracy of workpiece.
The invention provides a kind of without boron without phosphorus aluminium-alloy piston microemulsified working fluid, its raw material comprises following component by weight percentage: mineral oil 25-32%; Nonionogenic tenside 2-5%; Petroleum sodium sulfonate 2-4%; Assistant for emulsifying agent 3-6%; Amine 11-15%; Di-carboxylic acid 1-2%; Acid anhydrides 4-7%; Oiliness improver 5-8%; Anticorrosion and bactericidal agent 0.5-1%; Emulsified silicone oil defoamer 0.1-0.3% and water; The weight percent sum of described raw material is 100%.
In the present invention, described mineral oil plays lubrication in working fluid, and dissolves other oiliness improver.Mineral oil in the present invention is preferably paraffin base mineral oil or naphthenic mineral oil, and kinematic viscosity when being more preferably 40 DEG C is 10 ~ 20mm
2the paraffin base mineral oil of/s or naphthenic mineral oil, more easily more emulsified than full-bodied mineral oil, required emulsification dosage is less.
In the present invention, described nonionogenic tenside preferably for HLB value to be the alkylphenol polyoxyethylene of 6-9 and HLB value be in the fatty alcohol-polyoxyethylene ether of 6-9 one or more, this type of surfactant emulsifies ability is higher, stability in hard water can be better, antiacid, alkali and ionogen, lime soap dispersing power is stronger, and foam proneness is lower.Wherein, described alkylphenol polyoxyethylene preferred alkyl phenol polyethenoxy ether OP-4, described fatty alcohol-polyoxyethylene ether preferred fat polyoxyethylenated alcohol AEO-3.
In the present invention, described assistant for emulsifying agent is one or both in the Guerbet alcohol of carbonatoms 12 ~ 18 and alcohol ether, and have the ability promoting the emulsification of oily components in water, the Guerbet alcohol simultaneously also has the effect promoting lubrication.Wherein, the preferred carbonatoms of described Guerbet alcohol is the Guerbet alcohol of 12, the preferred butyl of described alcohol ether.
In the present invention, described amine is preferably alkanolamine, is more preferably one or more in trolamine, 2-amino-2-methyl-1-propanol and monoisopropanolamine.
In the present invention, described di-carboxylic acid is preferably 11 carbon di-carboxylic acid and/or 12 carbon di-carboxylic acid.
In the present invention, described acid anhydrides is preferably maleopimaric anhydride and/or Tetra hydro Phthalic anhydride.
In the present invention; react after one or more in described di-carboxylic acid and acid anhydrides mix with one or more in described amine and generate amine rust-preventive agent; this amine rust-preventive agent contains multiple hydroxyl and amide group; for hydrophilic polar group; larger affinity ability is had to metal; its non-polar group forms one deck hydrophobic protective layers at metallic surface oriented alignment, thus plays antirust effect.The amine rust-preventive agent that described reaction generates simultaneously has certain stability in hard water energy.
In the present invention, described oiliness improver is preferably one or both in vegetable oil acid and polyvalent alcohol synthetic ester, containing polar molecule, can form firmly adsorption film, can play good lubrication with metallic surface under the cutting speed of relative broad range.Wherein, the preferred trimethylolpropane tris oleic acid ester of described polyvalent alcohol synthetic ester.Meanwhile, described trimethylolpropane tris oleic acid ester has certain corrosion inhibition to aluminium alloy, the material that described vegetable oil acid and described amine hybrid reaction generate, and also has good corrosion inhibition to aluminium alloy.
In the present invention, described anticorrosion and bactericidal agent can adopt the anticorrosion and bactericidal agent of the various routine in this area, is preferably trihydroxy-perhydro-s-triazine and/or BIT.The consumption of described anticorrosion and bactericidal agent is preferably 0.8-1%, and described per-cent is weight percentage.
In the present invention, described emulsified silicone oil defoamer can adopt the emulsified silicone oil defoamer of the various routine in this area, is preferably the defoamer MS575 of German Meng Qingxin company.
In the present invention, described water is preferably industrial tap water.
Present invention also offers the described diluent without boron without phosphorus aluminium-alloy piston microemulsified working fluid, its extension rate is 10-40 times.Described extension rate refers to dilute the business of front strength of solution divided by the strength of solution gained after dilution.
Present invention also offers a kind of described preparation method without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it comprises following step:
(1) be that the water of 40 DEG C-50 DEG C mixes with described amine by temperature;
(2) mix with described di-carboxylic acid and described acid anhydrides successively, at 40 DEG C-50 DEG C, insulated and stirred is dissolved into liquid completely to solid, and uniform liquid is transparent;
(3) liquid step (2) obtained successively with described nonionogenic tenside, described petroleum sodium sulfonate, described oiliness improver, described assistant for emulsifying agent and described mineral oil, at 40 DEG C-50 DEG C, insulated and stirred is to mix and transparent;
(4) mix to liquid completely transparent with described anticorrosion and bactericidal agent and described emulsified silicone oil defoamer after the material that step (3) obtains being cooled to room temperature, to obtain final product.
In step (1), the time of described stirring is preferably more than 20 minutes.
In step (2), the time of described stirring is preferably more than 1 hour.
In step (3), the time of described stirring is preferably more than 2 hours.
In step (4), the time of described stirring is preferably more than 30 minutes.
Be sundown and transparent microemulsified working fluid without boron without phosphorus aluminium-alloy piston microemulsified working fluid described in the present invention.
Of the present inventionly can be applicable in the manufacturing procedure of aluminium-alloy piston without boron without phosphorus aluminium-alloy piston microemulsified working fluid or diluent, the manufacturing procedure of described aluminium-alloy piston is preferably the operations such as pin-and-hole roughing, external diameter roughing, machining of oil hole, annular groove processing, external diameter precision work or pin-and-hole precision work.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is:
1, microemulsified working fluid provided by the invention is not chloride, harmless; Not phosphorous, environmental protection and not easily raw bacterium is smelly; Not boracic, can not damage reproductive system; PH stability is good, long service life; There is outstanding stability in hard water energy and lubricity.
2, microemulsified working fluid of the present invention is different from emulsification working fluid, and cooling is better, can improve the working accuracy of workpiece.
3, microemulsified working fluid of the present invention is particularly useful for each operation of aluminium-alloy piston processing.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
The petroleum sodium sulfonate that the petroleum sodium sulfonate used in following embodiment is 50wt% for sodium sulfonate content.
Emulsified silicone oil defoamer is the defoamer MS575 of German Meng Qingxin company.
Embodiment 1
Described raw material by weight, at room temperature, 37.8 parts, industrial tap water is heated to 40 DEG C-50 DEG C, add trolamine 4 parts, monoisopropanolamine 7 parts, stir 20 minutes, then add 11 carbon di-carboxylic acid 1 part, Tetra hydro Phthalic anhydride 7 parts, insulated and stirred 1 is little dissolves completely up to solid, uniform liquid is transparent, add AEO-32 part successively while stirring again, petroleum sodium sulfonate 4 parts, vegetable oil acid 2 parts, trimethylolpropane tris oleic acid ester 3 parts, butyl 2 parts, C12 Guerbet alcohol 1 part, kinematic viscosity when 40 DEG C is 10mm
2the naphthenic mineral oil of/s 28 parts, insulated and stirred 2 is little of the complete homogeneous transparent of liquid, add hydroxyethyl perhydro-s-triazine 1 part after finally aforesaid liquid being down to room temperature, silicone emulsion defoamer MS5750.2 part, then stir 30 minutes to the complete homogeneous transparent of liquid.
The sundown obtained and homogeneous transparent liquid is microemulsified working fluid, this working fluid can dilute 10 ~ 40 times of uses as the case may be.The performance detection data of this working fluid, as shown in table 1.
Embodiment 2
Described raw material percentage, at room temperature, 30.8 parts, industrial tap water is heated to 40 DEG C-50 DEG C, add trolamine 6 parts, monoisopropanolamine 4 parts, 2-amino-2-methyl-1-propanol 3 parts, stir 20 minutes, add 11 carbon di-carboxylic acid 2 parts again, maleopimaric anhydride 4 parts, insulated and stirred 1 is little dissolves completely up to solid, uniform liquid is transparent, add AEO-33 part successively while stirring again, petroleum sodium sulfonate 3 parts, vegetable oil acid 2 parts, trimethylolpropane tris oleic acid ester 4 parts, butyl 4 parts, C18 Guerbet alcohol 1 part, when 40 DEG C, kinematic viscosity is 10mm
2the naphthenic mineral oil of/s 32 parts, insulated and stirred 2 is little of the complete homogeneous transparent of liquid, add hydroxyethyl perhydro-s-triazine 1 part after finally aforesaid liquid being down to room temperature, silicone emulsion defoamer MS5750.2 part, then stir 30 minutes to the complete homogeneous transparent of liquid.
The sundown obtained and homogeneous transparent liquid is microemulsified working fluid, this working fluid can dilute 10 ~ 40 times of uses as the case may be.The performance detection data of this working fluid, as shown in table 1.
Embodiment 3
Described raw material percentage, at room temperature, 32.3 parts, industrial tap water is heated to 40 DEG C-50 DEG C, add trolamine 6 parts, monoisopropanolamine 5 parts, 2-amino-2-methyl-1-propanol 4 parts, stir 20 minutes, add 12 carbon di-carboxylic acid 1 part again, maleopimaric anhydride 6 parts, insulated and stirred 1 is little dissolves completely up to solid, uniform liquid is transparent, add OP-44 part successively while stirring again, petroleum sodium sulfonate 3 parts, vegetable oil acid 3 parts, trimethylolpropane tris oleic acid ester 4 parts, butyl 4 parts, C12 Guerbet alcohol 1.5 parts, when 40 DEG C, kinematic viscosity is 20mm
2the paraffin base mineral oil of/s 25 parts, insulated and stirred 2 is little of the complete homogeneous transparent of liquid, add 1 part, BIT sterilant after finally aforesaid liquid being down to room temperature, emulsified silicone oil defoamer MS5750.2 part, then stir 30 minutes to the complete homogeneous transparent of liquid.
The sundown obtained and homogeneous transparent liquid is microemulsified working fluid, this working fluid can dilute 10 ~ 40 times of uses as the case may be.The performance detection data of this working fluid, as shown in table 1.
Embodiment 4
Described raw material percentage, at room temperature, 30.8 parts, industrial tap water is heated to 40 DEG C-50 DEG C, add trolamine 6 parts, monoisopropanolamine 5 parts, 2-amino-2-methyl-1-propanol 4 parts, stir 20 minutes, add 12 carbon di-carboxylic acid 2 parts again, Tetra hydro Phthalic anhydride 5 parts, insulated and stirred 1 is little dissolves completely up to solid, uniform liquid is transparent, add OP-45 part successively while stirring again, petroleum sodium sulfonate 2 parts, vegetable oil acid 3 parts, trimethylolpropane tris oleic acid ester 5 parts, butyl 4 parts, C12 Guerbet alcohol 2 parts, when 40 DEG C, kinematic viscosity is 20mm
2the paraffin base mineral oil of/s 25 parts, insulated and stirred 2 is little of the complete homogeneous transparent of liquid, add 1 part, BIT sterilant after finally aforesaid liquid being down to room temperature, emulsified silicone oil defoamer MS5750.2 part, then stir 30 minutes to the complete homogeneous transparent of liquid.
The sundown obtained and homogeneous transparent liquid is microemulsified working fluid, this working fluid can dilute 10 ~ 40 times of uses as the case may be.The performance detection data of this working fluid, as shown in table 1.
Table 1: embodiment products obtained therefrom performance index
From upper table 1, working fluid stoste prepared by embodiments of the invention, comparatively large-temperature range internal stability is good, can be preserved for a long time; And after above-mentioned stoste dilution, detect data presentation, rustless property, the aluminium corrosive nature of its diluent are splendid, and stability in hard water energy, antifoam performance are also fine.
Effect example 1
Certain piston factory used oil-in-water type working fluid (with A designate) ground finish piston external diameter originally, the diluent (with B designate) obtained after the microemulsified working fluid that rear section lathe uses the embodiment of the present invention 3 to develop dilutes 20 times, and through the contrast of 1 year, result was as follows:
1, working fluid A uses frowziness about half a year, bacterial detection content 10
6cfu/ml, needs to renew liquid; Without any abnormal taste when working fluid B used about half a year, bacterial detection content 10
2cfu/ml, uses 1 year detection bacteria content to be also only 10
4cfu/ml, does not still need to change liquid.
2, after using half a year, the water hardness of working fluid A and B is about 500ppm, a large amount of neat soap of working fluid A surface flotation and aluminium bits, and lathe also adheres to a lot of neat soap and aluminium bits, and piston external diameter grinding rear surface is even cut; Working fluid B outward appearance is without too large change, and working fluid B surface and lathe are without obvious neat soap and aluminium bits, and piston external diameter grinding rear surface also occurs from no marking.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1., without a boron without phosphorus aluminium-alloy piston microemulsified working fluid, its raw material comprises following component by weight percentage: mineral oil 25-32%; Nonionogenic tenside 2-5%; Petroleum sodium sulfonate 2-4%; Assistant for emulsifying agent 3-6%; Amine 11-15%; Di-carboxylic acid 1-2%; Acid anhydrides 4-7%; Oiliness improver 5-8%; Anticorrosion and bactericidal agent 0.5-1%; Emulsified silicone oil defoamer 0.1-0.3% and water; The weight percent sum of described raw material is 100%.
2. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: described mineral oil is paraffin base mineral oil or naphthenic mineral oil, kinematic viscosity when being preferably 40 DEG C is 10 ~ 20mm
2the paraffin base mineral oil of/s or naphthenic mineral oil.
3. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: the alkylphenol polyoxyethylene of described nonionogenic tenside to be HLB value be 6-9 and HLB value are one or more in the fatty alcohol-polyoxyethylene ether of 6-9; Described alkylphenol polyoxyethylene is preferably alkylphenol polyoxyethylene OP-4, and described fatty alcohol-polyoxyethylene ether is preferably fatty alcohol-polyoxyethylene ether AEO-3.
4. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: described assistant for emulsifying agent is one or both in the Guerbet alcohol of carbonatoms 12 ~ 18 and alcohol ether, described Guerbet alcohol is preferably the Guerbet alcohol of 12 for carbonatoms, and described alcohol ether is preferably butyl.
5. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: described amine is alkanolamine, is preferably one or more in trolamine, 2-amino-2-methyl-1-propanol and monoisopropanolamine; And/or described di-carboxylic acid is 11 carbon di-carboxylic acid and/or 12 carbon di-carboxylic acid; And/or described acid anhydrides is maleopimaric anhydride and/or Tetra hydro Phthalic anhydride.
6. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: described oiliness improver is one or both in vegetable oil acid and polyvalent alcohol synthetic ester, and described polyvalent alcohol synthetic ester is preferably trimethylolpropane tris oleic acid ester.
7. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: the petroleum sodium sulfonate of described petroleum sodium sulfonate to be sodium sulfonate content be more than 50wt%.
8. as claimed in claim 1 without boron without phosphorus aluminium-alloy piston microemulsified working fluid, it is characterized in that: described anticorrosion and bactericidal agent is trihydroxy-perhydro-s-triazine and/or BIT.
9. the diluent without boron without phosphorus aluminium-alloy piston microemulsified working fluid as described in any one of claim 1 ~ 8, is characterized in that: the extension rate of described diluent is 10-40 times.
10. the preparation method without boron without phosphorus aluminium-alloy piston microemulsified working fluid as described in any one of claim 1 ~ 8, it comprises following step:
(1) be that the water of 40 DEG C-50 DEG C mixes with described amine by temperature;
(2) mix with described di-carboxylic acid and described acid anhydrides successively, at 40 DEG C-50 DEG C, insulated and stirred is dissolved into liquid completely to solid, and uniform liquid is transparent;
(3) liquid step (2) obtained successively with described nonionogenic tenside, described petroleum sodium sulfonate, described oiliness improver, described assistant for emulsifying agent and described mineral oil, at 40 DEG C-50 DEG C, insulated and stirred is to mix and transparent;
(4) mix to liquid completely transparent with described anticorrosion and bactericidal agent and described emulsified silicone oil defoamer after the material that step (3) obtains being cooled to room temperature, to obtain final product.
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| CN105176646A (en) * | 2015-09-24 | 2015-12-23 | 国营第六一六厂 | Water-soluble soybean oil |
| CN107384542A (en) * | 2017-06-29 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of high wear-resistant Shock absorber oil composition |
| CN108774568A (en) * | 2018-05-25 | 2018-11-09 | 清华大学天津高端装备研究院 | A kind of semi-synthetic aluminium alloy working fluid and preparation method thereof |
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