CN105803165B - A kind of hardening media - Google Patents
A kind of hardening media Download PDFInfo
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- CN105803165B CN105803165B CN201610372834.4A CN201610372834A CN105803165B CN 105803165 B CN105803165 B CN 105803165B CN 201610372834 A CN201610372834 A CN 201610372834A CN 105803165 B CN105803165 B CN 105803165B
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/56—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering characterised by the quenching agents
- C21D1/60—Aqueous agents
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Abstract
The invention provides a kind of hardening media, by percentage to the quality, it contains following components：Zinc chloride：0.5‑10%；Sodium hydroxide：1‑15%；Saponification agent：0.01‑5%；Import quenches auxiliary agent：0.01‑5%；Water：Surplus.Hardening media of the present invention has higher cooling velocity, about 338 DEG C/s in hot stage；In the about 102 DEG C/s of cooling velocity of cold stage, this can effectively prevent the cracking of component, and composition is simple, be easy to preparation, low toxic and environment-friendly, cost are low, easily operated, inhibition efficiency is high, with good application prospect.
Description
Technical field
The present invention relates to metal heat treatmet field, more particularly to a kind of aqueous hardening media.
Background technology
In order to improve the performance of the metal material such as steel, it is necessary to be heat-treated to the workpiece of metal material, commonly use
Technology for Heating Processing have the heat treatment methods such as quenching, tempering, annealing, normalizing.Wherein, the quenching of steel is that steel is heated into stagnation temperature
Ac3 (sub-eutectoid steel) or Ac1 (hypereutectoid steel) temperatures above is spent, insulation a period of time, all or part of austenitizing is allowed to, so
Below Ms (or isothermal near Ms) is as cold as with the cooling rate more than critical cooling rate soon afterwards and carries out martensite (or bainite) transformation
Technology for Heating Processing.During quenching, the cooling procedure of workpiece is generally divided into three phases, i.e. metal material and is quenched Jie
The first stage (steam mem stage) of the steam encirclement of matter, the second stage (boiling stage) of vapor film breakage boiling, metal material
The temperature of material reaches that the boiling point of hardening media captures the phase III (convection current stage) of heat below by way of convection current, is then cooled
To room temperature.Generally also by the solution treatment of the materials such as aluminium alloy, copper alloy, titanium alloy, safety glass or with quick cooled
The Technology for Heating Processing of journey is referred to as quenching.The property such as the intensity of steel, hardness, wearability, fatigue strength and toughness after quenching
It can be greatly improved, so as to meet the different use requirements of various machine components and instrument.Quenching can also be passed through
Meet the special physics such as ferromagnetism, the corrosion resistance of some special steel materials, chemical property.
At present, the characteristics of conventional hardening media has water-based quenching agent and oiliness quenching medium, water-based quenching agent is whole
All there is very high cooling velocity in cooling procedure, can promote to form crystal grain tiny in High-temperature cooling stage high cooling velocity
Workpiece, be conducive to improving the final performance of workpiece, but in cold stage, too fast cooling velocity makes the internal stress mistake of workpiece
Greatly, thus be easily caused workpiece cracking.It is the cooling of whole cooling stage compared with water-based quenching agent, the characteristics of oiliness quenching medium
Speed is slow, although can prevent workpiece in cold stage because internal stress is excessive and causes cracking, but be due to that hot stage is cold
But speed is slower, therefore is easily caused that workpiece crystal grain is larger, the performance after reduction workpiece quenching.In addition, traditional oiliness quenching
Agent is oily generally based on the mineral oil with petroleum distillate, is equipped with additive and forms.The distinctive performance of mineral oil is determined
Substantial amounts of smog can be produced in quenching, therefore easily pollutes environment, environment-friendly function is poor.Moreover, based on mineral oil
Oiliness quenching medium cooling velocity narrow range, the flash-point of mineral oil is low, easily triggers fire, using dangerous.Applied to building row
The rolled steel dosage and specification in the fields such as industry, science of bridge building are continuously increased.But steel easily exist during storage, transport and use
Rust corrosion in the surrounding mediums such as carbon dioxide, oxygen gas and water, acid.Corrosion is not only caused outside the waste of steel, influence steel
See, and the potential safety hazard that produces and live can be caused.
Therefore the formula by improving existing hardening media is needed, it is made steel workpiece excellent in mechanical performance,
And can effectively suppress the corrosion of steel workpiece.
The content of the invention
The invention provides a kind of hardening media, by percentage to the quality, it contains following components：Zinc chloride：0.5-
10%；Sodium hydroxide：1-15%；Saponification agent：0.01-5%；Import quenches auxiliary agent：0.01-5%；Water：Surplus.
Mode is preferably carried out as the present invention, by percentage to the quality, the saponification agent contains following components：Nonionic
Surfactant：3-5%；Anion surfactant：4.5-10%；Wandering agent：4-8%；Anhydrous sodium sulfate：Surplus.
Mode is preferably carried out as the present invention, it is characterised in that the nonionic surfactant is selected from C12-C18
AEO, C12-C14 APGs, the contracting of C12-C18 alcohol and ethylene oxide/propylene oxide block copolymer
The mixture of any one or more than two kinds in compound, C8-C20 branched-chain alcoho APEOs；The anion surface active
Agent be selected from：C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonates, C12-C18 alkyl alkoxy sulfates, α-alkenyl sulphur
The mixture of any one or more than two kinds in sour sodium, C14-C18 MESs.
Be preferably carried out mode as the present invention, the nonionic surfactant be cetanol APEO -20 or
Ethoxylated dodecyl alcohol -10, and the anion surfactant is neopelex or coconut acyl methyl ox sulphur
Sour sodium.
Mode is preferably carried out as the present invention, the wandering agent is selected from sodium silicoaluminate, sodium metasilicate, montmorillonite, dioxy
The combination of any one or more than two kinds in SiClx.
Mode is preferably carried out as the present invention, the wandering agent is the combination mixture of sodium metasilicate and sodium-based montmorillonite.
Mode is preferably carried out as the present invention, the import quenching auxiliary agent includes carboxymethyl cellulose, molybdate, carbonic acid
Salt, orthophosphates, nitrite, tungstates, benzoate, indoles hydrochlorate, citrate and alginate.
Mode is preferably carried out as the present invention, the import quenching auxiliary agent is selected from carboxymethyl cellulose, sodium molybdate, carbon
The group of any one or more than two kinds in sour sodium, ammonium tungstate, sodium benzoate, indolebutyric acid sodium, sodium citrate and sodium alginate
Close.
Mode is preferably carried out as the present invention, by percentage to the quality, the import quenching auxiliary agent contains following components：
Carboxymethyl cellulose：20-60%；Sodium molybdate：1-15%；Sodium carbonate：1-15%；Indolebutyric acid sodium：50-70%.
Present invention also offers a kind of application of any one hardening media recited above in metal heat treatmet field.
Hardening media of the present invention has higher cooling velocity, about 338 DEG C/s in hot stage；In cold stage cooling
Speed is relatively slow, about 102 DEG C/s, and this can prevent too fast cooling, contribute to crystal grain thinning, it is to avoid workpiece ftractures；This
Also there is excellent salt fog resistance outside.So the hardening media that the present invention is provided has, composition is simple, be easy to preparation, low toxicity ring
The advantages of guarantor, low, easily operated cost and high inhibition efficiency.
Embodiment
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of art of the present invention
The identical implication that art personnel are generally understood that.When there is contradiction, the definition in this specification is defined.
The participation in the election detailed description of the invention below for being preferable to carry out method and including embodiment this public affairs can be more easily understood
Open content.Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering is non-
It is exclusive including.Wanted for example, composition, step, method, product or device comprising listed elements are not necessarily limited to those
Element, but can include not expressly listed other key elements or such a composition, step, method, product or device it is intrinsic
Key element.
Temperature, time or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value is limited, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether whether the scope separately discloses.For example, when open
During scope " 1-5 ", described scope should be interpreted as including scope " 1-4 ", " 1-3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3
With 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end value and at this
In the range of all integers and fraction.In the case of not conflicting, those skilled in the art can be by this specification
The feature of different embodiments, embodiment or the example and different embodiments of description, embodiment or example be combined and
Combination.
In the description of this specification, reference term " one is preferably carried out scheme ", " some are preferably carried out scheme ",
The description of " preferably scheme ", " example " or " some examples " etc. means to combine the specific spy that the embodiment or example are described
Levy, structure, material or feature are contained at least one embodiment of the present invention or example.In this manual, to above-mentioned
The schematic representation of term is necessarily directed to identical embodiment or example.Moreover, the specific features of description, structure, material
Material or feature can in an appropriate manner be combined in any one or more embodiments or example.In addition, not conflicting
In the case of, those skilled in the art can be by the not be the same as Example or example and non-be the same as Example described in this specification
Or the feature of example is combined and combined.
It is an object of the invention to provide a kind of hardening media, by percentage to the quality, its formula contains following components：
Zinc chloride：0.5-10%；
Sodium hydroxide：1-15%；
Saponification agent：0.01-5%；
Import quenches auxiliary agent：0.01-5%；
Water：Surplus.
Zinc chloride：
The zinc chloride is one of main functional component of hardening media of the present invention, be inorganic chemicals industry staple product it
One, its application is extremely wide.Zinc chloride is white particulate, bar-shaped or powder.Odorlessness.It is soluble in water, it is dissolving in solid salt
Maximum (25 °C, 333g/100g) are spent, its reason is dissolved in water formation complex acid H [ZnCl2(OH)].Be dissolved in methanol, it is ethanol, sweet
Oil, acetone, ether, insoluble in liquefied ammonia.Hygroscopy is strong, can absorb moisture from air and deliquescence.With dissolving metal oxide
With the characteristic of cellulose.Melting zinc chloride has good electric conductivity.There is dense white cigarette generation when scorching hot.The zinc chloride can
It is made by zinc or zinc oxide with being crystallized after hydrochloric acid reaction.
Sodium hydroxide：
The sodium hydroxide is one of main functional component of hardening media of the present invention, and chemical formula is NaOH, be commonly called as caustic soda,
Caustic soda, caustic soda, are a kind of highly basic with severe corrosive, generally sheet or particle shape, soluble in water, are put when being dissolved in water
Heat, and alkaline solution is formed, separately there are vapor generation deliquescence and carbon dioxide in hygroscopy, easy draw air to occur rotten,
Hydrochloric acid can be added to check whether to go bad.Sterling is the crystal of water white transparency.Density 2.130g/cm3.318.4 DEG C of fusing point.Boiling point
1390℃.Industrial goods contain a small amount of sodium chloride and sodium carbonate, are the crystal of White-opalescent.There are bulk, sheet, granular and rod
Shape etc..
Sodium hydroxide can will be completely dissociated into sodium ion and hydroxide ion in water, with the CO in air2Reaction generation carbon
Sour sodium, sodium chloride and zinc hydroxide can be generated with zinc chloride reaction, and zinc hydroxide is dissolved in sodium hydroxide and obtains sodium zincate and water again.
Saponification agent：
Saponification agent of the present invention contains following components：Nonionic surfactant：3-5%；Anion surfactant：
4.5-10%；Wandering agent：4-8%；Anhydrous sodium sulfate：Surplus.
The nonionic surfactant mainly includes polyoxyethylene-type, polyol type, alkylolamides type.
The anion surfactant is the negatively charged surface in part that surface-active action is played after being ionized in water
Activating agent, it is big from structure anion surfactant to be divided into soap, sulfonate, sulfuric acid and phosphate ester salt four
Class.
The wandering agent is soluble in water, is ecru lotion or white powder, can prevent powdery paints from luming.
The anhydrous sodium sulfate is monoclinic system, and crystal short cylinder, aggregate is colourless in compact massive or cot shape etc.
It is bright, it is soluble in water sometimes with pale yellow or green.White, odorless, the crystallization for having bitter taste or powder, there is hygroscopicity.Profile is nothing
Color, transparent, big crystallization or graininess little crystallization.Easy moisture absorption turns into aqueous sulfuric acid sodium in air.
It is preferably carried out in the present invention in mode, the nonionic surfactant is selected from C12-C18 fatty alcohol polyoxy
Vinethene, C12-C14 APGs, condensation product, the C8-C20 of C12-C18 alcohol and ethylene oxide/propylene oxide block copolymer
The mixture of any one or more than two kinds in branched-chain alcoho APEO.
It is preferably carried out in the present invention in mode, the nonionic surfactant is selected from cetostearyl alcohol polyoxyethylene
Ether -6, ceteareth-12, ceteareth-20, cetostearyl alcohol APEO -25,
Cetanol APEO -10, cetanol APEO -20, laruyl alcohol are poly-, oxygen vinethene -4, ethoxylated dodecyl alcohol -
5th, ethoxylated dodecyl alcohol -9, ethoxylated dodecyl alcohol -10, ethoxylated dodecyl alcohol -12, lauryl alcohol polyethylene glycol oxide
Ether -15, ethoxylated dodecyl alcohol -20, ethoxylated dodecyl alcohol -23, Brij -10, oleic alcohol polyoxyethylene
Ether-20, Brij-721-10, Brij-721-20, Brij-721-100；Coconut oleoyl amine third
Any one or a few mixing in base hydroxyl sulphonic acid betaine, cocoamidopropyl dimethyl glycine betaine.
It is preferably carried out in the present invention in mode, the anion surfactant is to be selected from：C12-C18 fatty acid soaps,
C11-C18 alkylbenzenesulfonates, C12-C18 alkyl alkoxy sulfates, α-sodium olefin sulfonate, C14-C18 fatty acid methyl ester sulphurs
The mixture of any one or more than two kinds in hydrochlorate.
It is preferably carried out in the present invention in mode, the anion surfactant is selected from：Neopelex, ten
Dialkyl diphenyl ether sodium disulfonate, fatty alcohol sodium isethionate, polyxyethylated allyl phenyl ether sulfuric acid, acid amides
Base APEO magnesium sulfate, 1-isobutyl-3,5-dimethylhexylphosphoric acid sylvite, Dodecyl Polyoxyethylene Ether sulfosuccinate disodium, α-alkenyl
Any one or a few mixing in sodium sulfonate, coconut acyl methyl taurine sodium.
It is preferably carried out in the present invention in mode, the wandering agent is selected from sodium silicoaluminate, sodium metasilicate, montmorillonite, titanium dioxide
The combination of any one or more than two kinds in silicon.
The wandering agent is all solid powder state, and the average grain diameter of powder is less than 10 microns.
It is preferably carried out in the present invention in mode, the wandering agent is the composition of sodium metasilicate and sodium-based montmorillonite, and institute
The mass ratio for stating sodium metasilicate and sodium-based montmorillonite is 2：1.
It is preferably carried out in the present invention in mode, by percentage to the quality, the saponification agent contains following components：Nonionic
Surfactant：3-5%；Anion surfactant：4.5-10%；Wandering agent：4-8%；Anhydrous sodium sulfate：Surplus.
It is preferably carried out in the present invention in mode, by percentage to the quality, the saponification agent contains following components：Nonionic
Surfactant：3-5%；Anion surfactant：6-8%；Wandering agent：5-7%；Anhydrous sodium sulfate：Surplus.
Be preferably carried out in the present invention in mode, the nonionic surfactant be cetanol APEO -20 or
Ethoxylated dodecyl alcohol -10, and the anion surfactant is neopelex or coconut acyl methyl ox sulphur
Sour sodium.
It is preferably carried out in the present invention in mode, saponification agent of the present invention is prepared via a method which to obtain：
（1）The anion surfactant and anhydrous sodium sulfate of formula ratio are added in 65-70 DEG C of deionized water, stirring is equal
Even, the pH value that mixed slurry is adjusted with citric acid or ammoniacal liquor is 7.5-8.5, obtains mixed slurry；
（2）The mixed slurry is displayed and filtered after 5-10h, saponification agent original washing powder is obtained by being spray-dried；
（3）Saponification agent original washing powder is uniformly mixed with nonionic surfactant, wandering agent, that is, obtains saponification agent.
Wherein, the quality solid content of the mixed slurry is controlled in the range of 65-70%, the temperature control of the mixed slurry
System is in the range of 65-70 DEG C.
Import quenches auxiliary agent：
Import quenching auxiliary agent of the present invention includes carboxymethyl cellulose, molybdate, carbonate, orthophosphates, nitrous acid
Salt, tungstates, benzoate, indoles hydrochlorate, citrate and alginate.
The carboxymethyl cellulose, also known as sodium carboxymethylcellulose, abbreviation CMC, be in the world today using it is widest in area,
The maximum cellulose species of consumption.By the cellulose derivative of carboxymethyl substituent, with naoh treatment cellulose formation alkali
Cellulose, then be made with monochloroacetic acid reaction.Sodium carboxymethylcellulose（CMC）Belong to anionic cellulose ethers, outward appearance is white
Color or slightly yellow wadding fibrous powder or white powder, odorless, tasteless are nontoxic；Cold water or hot water are soluble in, being formed has necessarily
The clear solution of viscosity.Solution is neutral or alkalescence, solvable insoluble in ethanol, ether, isopropanol, acetone and other organic solvent
In aqueous 60% ethanol or acetone soln.
The molybdate includes sodium molybdate and/or calcium molybdate；The carbonate includes sodium carbonate and/or calcium carbonate；It is described
Orthophosphates includes ammonium phosphate and/or sodium phosphate；The nitrite is natrium nitrosum；The tungstates include sodium tungstate and/
Or artificial schellite；The benzoate is sodium benzoate；The indoles hydrochlorate includes heteroauxin sodium, indolepopionic acid sodium, indoles fourth
Sour sodium and/or butyric acid potassium；The citrate is sodium citrate；The alginate is sodium alginate.
It is preferably carried out in the present invention in mode, the import quenching auxiliary agent is selected from carboxymethyl cellulose, sodium molybdate, carbon
The combination of any one or more than two kinds in sour sodium, sodium benzoate, indolebutyric acid sodium, sodium citrate.
It is preferably carried out in the present invention in mode, by percentage to the quality, the import quenching auxiliary agent contains following components：
Carboxymethyl cellulose：20-60%；Sodium molybdate：1-15%；Sodium carbonate：1-15%；Indolebutyric acid sodium：50-70%.
It is preferably carried out in the present invention in mode, by percentage to the quality, the import quenching auxiliary agent contains following components：
Carboxymethyl cellulose：25%；Sodium molybdate：5%；Sodium carbonate：10%；Indolebutyric acid sodium：60%.
Present invention also offers a kind of method for preparing the hardening media, it is comprised the following steps：
（1）By the larger component of particle in formula by broken, grinding and screening, it is made powdered；
（2）Add above-mentioned dusty raw materials and other components raw material while stirring in the water of formula ratio, be well mixed
.
After red-hot workpiece enters hardening media of the present invention, in 650~500 DEG C of high-temperature region, workpiece surface
Around water be heated rapidly, vaporize and form steam blanket, because steam is the non-conductor of heat, it constrains water in high-temperature region cooling
The performance of ability, therefore the cooling velocity of workpiece declines rapidly；Meanwhile, sodium salt, zinc salt in hardening media etc. are analysed in workpiece surface
Go out, and be heated, burst, so as to tear steam blanket, then the water in hardening media is contacted with workpiece surface again, re-forms steaming
Steam film, such iterative cycles.The low-temperature space below 300 DEG C, the zinc chloride crystal that workpiece surface is separated out is increased by import quenching auxiliary agent
Thickness is strengthened, and the deposit that workpiece surface is produced no longer is produced explosion, the steam blanket of formation can not be torn again, therefore deposit
Plus steam blanket serves the good dual heat-blocking action of solid vapour.
In addition, the unexpected discovery of the present inventor, the saponification agent coordinates import quenching auxiliary agent effectively to reduce quenching
Deformation and cracking, and steel is possessed good corrosion resistance, thus it is speculated that it is that saponification agent coordinates import quenching auxiliary agent can the reason for possible
To promote steel surface formation layer protecting film, cooling stability and cooling velocity of the hardening media in high temperature are improved, and
The cooling velocity for slowing down workpiece can also be stablized in cold stage, to prevent too fast cooling, so as to avoid workpiece cracking.
In addition the anti-corrosion component contained in import quenching auxiliary agent can improve the stabilization of diaphragm except that can improve the corrosion resistance of metal
Property.
Hardening media of the present invention can apply to metal heat treatmet field, and steel component is quenched.
Hardening media of the present invention is applied to carbon steel and structural alloy steel.The structural alloy steel can be divided into commonly
Structural alloy steel and specific use structural alloy steel.The former includes Hi-Stren steel, cryogenic steel, unimach, oozed
Carbon steel, quenched and tempered steel and non-hardened and tempered steel；The latter includes spring steel, ball-bearing steel, automatic steel, cold punching compressed steel etc..These steel
It is required that with higher yield strength, tensile strength and fatigue strength, also enough plasticity and toughness.The structural alloy steel
It is widely used in the structures such as ship, vehicle, aircraft, guided missile, weapons, railway, bridge, pressure vessel, lathe.It is of the present invention to quench
Fiery medium is best suitable for processing and requires higher steel to corrosion resistance, can obtain high-performance corrosion-resisting steel.Quenching of the present invention is situated between
Matter helps to improve the tissue morphology of corrosion-resisting steel, refines austenite structure, prevents or delays carbon too early in cooling procedure
Separate out, make its diffusional precipitation in ferrite, improve its intensity.
In actual production, for certain specific standard and the anti-corrosion product made from steel of purposes, it is necessary to reasonably determine cooled
The technological parameter of journey, to obtain required institutional framework.The temperature in use of hardening media of the present invention should be controlled 25~50
Within DEG C, temperature control can be carried out using cooling water cooling or by the hydronic method of hardening media.
Hardening media of the present invention has that composition is simple, is easy to preparation, low toxic and environment-friendly, cost are low, easily operated and slow
The advantages of losing efficiency high, with good application prospect.
The present invention is explained in more detail below by some embodiments and embodiment, comparative example, it should be appreciated that
It is that these embodiments are merely exemplary and nonrestrictive.
Embodiment 1, a kind of hardening media, by percentage to the quality, it contains following components：Zinc chloride：0.5-10%；
Sodium hydroxide：1-15%；Saponification agent：0.01-5%；Import quenches auxiliary agent：0.01-5%；Water：Surplus.
Embodiment 2, identical with embodiment 1, difference is, by percentage to the quality, and the saponification agent contains following
Component：Nonionic surfactant：3-5%；Anion surfactant：4.5-10%；Wandering agent：4-8%；Anhydrous sodium sulfate：It is remaining
Amount.
Embodiment 3, identical with embodiment 2, difference is, the nonionic surfactant is selected from C12-C18
AEO, C12-C14 APGs, the contracting of C12-C18 alcohol and ethylene oxide/propylene oxide block copolymer
The mixture of any one or more than two kinds in compound, C8-C20 branched-chain alcoho APEOs；The anion surface active
Agent be selected from：C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonates, C12-C18 alkyl alkoxy sulfates, α-alkenyl sulphur
The mixture of any one or more than two kinds in sour sodium, C14-C18 MESs.
Embodiment 4, identical with embodiment 2, difference is, the nonionic surfactant is cetanol polyoxy second
Alkene ether -20 or ethoxylated dodecyl alcohol -10, and the anion surfactant is neopelex or coconut acyl
N-methyltaurine sodium.
Embodiment 5, identical with embodiment 2, difference is, the wandering agent is selected from sodium silicoaluminate, sodium metasilicate, illiteracy
The combination of any one or more than two kinds in de- soil, silica.
Embodiment 6, identical with embodiment 2, difference is, the wandering agent is the group of sodium metasilicate and sodium-based montmorillonite
Close mixture.
Embodiment 7, identical with embodiment 1, difference is, import quenching auxiliary agent include carboxymethyl cellulose,
Molybdate, carbonate, orthophosphates, nitrite, tungstates, benzoate, indoles hydrochlorate, citrate and alginate.
Embodiment 8, identical with embodiment 1, difference is, the import quenching auxiliary agent is selected from carboxymethyl cellulose
In element, sodium molybdate, sodium carbonate, ammonium tungstate, sodium benzoate, indolebutyric acid sodium, sodium citrate and sodium alginate any one or
More than two kinds of combination.
Embodiment 9, identical with embodiment 1, difference is, by percentage to the quality, and the import quenching auxiliary agent contains
There is following components：Carboxymethyl cellulose：20-60%；Sodium molybdate：1-15%；Sodium carbonate：1-15%；Indolebutyric acid sodium：50-70%.
Application of any one hardening media in metal heat treatmet field in embodiment 10, a kind of embodiment 1-9.
Specific embodiment and for example no specified otherwise of the raw material that comparative example is used are commercially available below, wherein, anhydrous sulphur
Sour sodium is purchased from the rising sun Trade Co., Ltd. of Shanghai hundred million；Complex silicate sodium is purchased from Qingdao Dongyue Sodium Silicate Co., Ltd.；Sodium-based montmorillonite
Purchased from Zhejiang Fenghong New Material Co., Ltd.；Carboxymethyl cellulose is purchased from Jinzhou City Hong Hai celluloses Co., Ltd；Indoles
Sodium butyrate is purchased from Zhengzhou Yin Hai Chemical Co., Ltd.s, wherein：
A-1：Saponification agent：By percentage to the quality, it contains 4% ethoxylated dodecyl alcohol -10,7% detergent alkylate sulphur
Sour sodium, 4% complex silicate sodium, 2% sodium-based montmorillonite and 83% anhydrous sodium sulfate；It is prepared via a method which to obtain：
（1）The neopelex and anhydrous sodium sulfate of formula ratio are added in 65 DEG C of deionized waters, is stirred,
PH value with citric acid or ammoniacal liquor regulation mixed slurry is 8.0, obtains the mixed slurry that quality solid content is 68 %；
（2）By step（1）The mixed slurry of acquisition is displayed and filtered after 7h, and saponification agent original washing powder is obtained by being spray-dried；
（3）By step（2）The saponification agent original washing powder of acquisition and nonionic surfactant ethoxylated dodecyl alcohol -10, silicon
Sour sodium, sodium-based montmorillonite, which are uniformly mixed, obtains saponification agent.
A-2：Saponification agent：By percentage to the quality, it contains 4% ethoxylated dodecyl alcohol -10,7% detergent alkylate sulphur
Sour sodium, 6% complex silicate sodium and 83% anhydrous sodium sulfate；Preparation method is identical with A-1 saponification agents, and difference is no sodium-based montmorillonite
Composition.
A-3：Saponification agent：By percentage to the quality, it contains 5% cetanol APEO -20,10% detergent alkylate sulphur
Sour sodium, 6% complex silicate sodium, 2% sodium-based montmorillonite and 77% anhydrous sodium sulfate；Preparation method is identical with A-1 saponification agents, and difference exists
In nonionic surfactant be cetanol APEO -20.
B-1：Import quenches auxiliary agent：By percentage to the quality, it contains：25% carboxymethyl cellulose；5% sodium molybdate；10% carbon
Sour sodium；60% indolebutyric acid sodium.
B-2：Import quenches auxiliary agent：By percentage to the quality, it contains：55% carboxymethyl cellulose；5% sodium molybdate；10% carbon
Sour sodium；30% indolebutyric acid sodium.
B-3：Import quenches auxiliary agent：By percentage to the quality, it contains：85% carboxymethyl cellulose；5% sodium molybdate；10% carbon
Sour sodium.
B-4：Import quenches auxiliary agent：By percentage to the quality, it contains：25% carboxymethyl cellulose；5% ammonium tungstate；10% carbon
Sour sodium；30% sodium benzoate；30% sodium citrate.
The preparation method of example 1 below -10 and comparative example 1-5 hardening medias, is comprised the following steps：
（1）By the larger component of particle in formula by broken, grinding and screening, it is made powdered；
（2）Add above-mentioned dusty raw materials and other components raw material while stirring in the deionized water of formula ratio, mix
Close uniform.
Following test and evaluation is carried out to example 1 below -10 and comparative example the 1-5 hardening media obtained：
（1）It is situated between using model ZH9667 " material critical temperature and continuous cooling curve measuring and analysing meter " test quenching
Cooling velocity of the matter in the case where different temperatures is interval.
（2）According to 45# steel specified in GB/T699-1999 standards recommend heat treating regime 850 DEG C of normalizings, 840 DEG C quench
Fire, the condition of 600 DEG C of tempering are handled, and thickness is put into each hardening media for 45mm 45# steel plates, steel plate after measurement quenching
The case hardness of sample（HRC）It is worth and observes whether it has cracking phenomena, as a result such as table 1.
（3）Will be by test（2）After the 40Cr steel plate samples of processing are cleaned with warm water, its corrosion resistance is tested；Specifically join
Examine standard GB/T/T10125-1997, salt spray test solution：NaCl and distilled water are prepared.The concentration of solution is 50 ± 5 g/L,
PH value is 6.5~7.2, and the temperature inside the box is 35 ± 2 DEG C, and salt fog settling amount is the cm of 1.0~2.0 ml/802h；Salt spray test side
Method：Steel plate sample is placed in salt fog cabinet straight at 30-45 ° of direction, and 24 h of continuous spraying are a cycle, sprays 1 respectively
With 2 cycles.After experiment terminates, it is placed on Indoor Natural and dries 0.5~1 h, then cleaned with room temperature water, and dries up immediately,
With the mm grids of 3 mm × 3 measurement sample rate of corrosion, as a result such as table 1.
Embodiment 1：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-1；3g imports
Quench auxiliary agent B -1；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
341.1 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 100.6 DEG C/s.
Embodiment 2：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-2；3g imports
Quench auxiliary agent B -1；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
340.6 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 107.3 DEG C/s.
Embodiment 3：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-3；3g imports
Quench auxiliary agent B -1；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
342.7 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 102.6 DEG C/s.
Embodiment 4：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-1；3g imports
Quench auxiliary agent B -2；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
338.8 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 110.1 DEG C/s.
Embodiment 5：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-1；3g imports
Quench auxiliary agent B -3；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
333.2 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 108.9 DEG C/s.
Embodiment 6：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-1；3g imports
Quench auxiliary agent B -4；88g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
328.4 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 112.3 DEG C/s.
Embodiment 7：
Hardening media is prepared according to following formula：7g zinc chloride；8g sodium hydroxides；2.5g saponification agents A-1；3.5g import
Quench auxiliary agent B -1；79g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
343.2 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 99.8 DEG C/s.
Embodiment 8：
Hardening media is prepared according to following formula：7g zinc chloride；8g sodium hydroxides；2.5g saponification agents A-1；3.5g import
Quench auxiliary agent B -2；79g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
323.7 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 109.7 DEG C/s.
Embodiment 9：
Hardening media is prepared according to following formula：7g zinc chloride；8g sodium hydroxides；2.5g saponification agents A-1；3.5g import
Quench auxiliary agent B -3；79g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
330.5 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 107.2 DEG C/s.
Embodiment 10：
Hardening media is prepared according to following formula：7g zinc chloride；8g sodium hydroxides；2.5g saponification agents A-1；3.5g import
Quench auxiliary agent B -4；79g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
329.6 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 108.9 DEG C/s.
Comparative example 1：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；1.5g saponification agents A-1；91g go from
Sub- water.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
175.4 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 88.0 DEG C/s.
Comparative example 2：
Hardening media is prepared according to following formula：3.5g zinc chloride；4g sodium hydroxides；3g imports quench auxiliary agent B -1；
89.5g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
189.2 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 90.6 DEG C/s.
Comparative example 3：
Hardening media is prepared according to following formula：10g sodium chloride；8g potassium chloride；8g sodium nitrate；74g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
145.1 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 121.6 DEG C/s.
Comparative example 4：
Hardening media is prepared according to following formula：3g polyethers（Molecular weight is 38000）；6g isopropanolamines；1.2g sodium molybdate；
0.5g fluorine silicon defoaming agents；89.3g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
176.5 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 105.6 DEG C/s.
Comparative example 5：
Hardening media is prepared according to following formula：45g polyethers（Molecular weight is 50000）；5g isopropanolamines；1g sodium molybdates；
1.2g fluorine silicon defoaming agents；47.8g deionized waters.
Measured through experiment, high-temperature region of the hardening media that the present embodiment is provided more than 400 DEG C, maximum cooling velocity is
132.2 DEG C/s, the low-temperature space below 400 DEG C, most fast cooling velocity is 95.4 DEG C/s.
Table 1
Cooling of the hardening media in hot stage in the cooling velocity and above-mentioned data of hardening media, comparative example
Speed is relatively slow, is accelerated relatively in cold stage cooling velocity.And hardening media of the embodiment of the present invention hot stage have compared with
High cooling velocity, about 338 DEG C/s；And it is relatively slow in cold stage cooling velocity, about 102 DEG C/s, cool time extension,
Too fast cooling is effectively prevented, contributes to crystal grain thinning, so as to avoid workpiece cracking.Compared with comparative example, the present invention
Embodiment hardening media also has more preferable salt fog resistance.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
The scope as wide as possible for requiring to be contemplated that is intended to, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology by formed language performance it is inaccurate due to and not
The possible equivalent that is presently considered or son are replaced, and these changes should also be interpreted in the conceived case it is appended
Claim covering.
Claims (2)
1. a kind of hardening media, it is characterised in that by percentage to the quality, it contains following components：
Zinc chloride：7%；
Sodium hydroxide：8%；
Saponification agent：2.5%；
Import quenches auxiliary agent：3.5%；
Water：Surplus；
The saponification agent：By percentage to the quality, it contains 4% ethoxylated dodecyl alcohol -10,7% DBSA
Sodium, 4% complex silicate sodium, 2% sodium-based montmorillonite and 83% anhydrous sodium sulfate；It is prepared via a method which to obtain：
(1) neopelex and anhydrous sodium sulfate of formula ratio are added in 65 DEG C of deionized waters, stirs, uses lemon
The pH value of lemon acid or ammoniacal liquor regulation mixed slurry is 8.0, obtains the mixed slurry that quality solid content is 68%；
(2) mixed slurry for obtaining step (1) is displayed and filtered after 7h, and saponification agent original washing powder is obtained by being spray-dried；
(3) the saponification agent original washing powder and the nonionic surfactant ethoxylated dodecyl alcohol -10 that obtain step (2), sodium metasilicate,
Sodium-based montmorillonite, which is uniformly mixed, obtains saponification agent；
The import quenches auxiliary agent：By percentage to the quality, it contains：25% carboxymethyl cellulose；5% sodium molybdate；10% carbon
Sour sodium；60% indolebutyric acid sodium.
2. application of the hardening media in metal heat treatmet field described in claim 1.
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| CN108441607A (en) * | 2018-03-20 | 2018-08-24 | 郑州正赢石化有限公司 | Environment-friendly type rolled hardening liquid |
| CN108754094A (en) * | 2018-05-24 | 2018-11-06 | 合肥汇之新机械科技有限公司 | A kind of low-carbon alloy steel water-soluble quenching medium and preparation method thereof |
| CN109161662A (en) * | 2018-11-27 | 2019-01-08 | 徐州市恩矿新材料有限公司 | A kind of quenching medium of wear-resistant material |
| CN110016542A (en) * | 2019-04-17 | 2019-07-16 | 南宁学院 | Quenching Medium for Heat Treatment |
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