CN105803165A - Quenching medium - Google Patents
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- CN105803165A CN105803165A CN201610372834.4A CN201610372834A CN105803165A CN 105803165 A CN105803165 A CN 105803165A CN 201610372834 A CN201610372834 A CN 201610372834A CN 105803165 A CN105803165 A CN 105803165A
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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 quenching medium. The quenching medium is prepared from, by mass, 0.5-10% of zinc chloride, 1-15% of sodium hydroxide, 0.01-5% of a saponifying agent, 0.01-5% of imported quenching auxiliaries and the balance water. The quenching medium has a high cooling speed at the high-temperature stage, and the cooling speed is about 338 DEG C/s; the cooling speed is about 102 DEG C/s at the low-temperature stage; and therefore cracking of components can be effectively prevented, ingredients are simple, preparation is easy, and the quenching medium is low in toxin, environment-friendly, low in cost, easy to operate and high in corrosion inhibiting efficiency and has good application prospects.
Description
Technical field
The present invention relates to metal heat treatmet field, particularly to a kind of aqueous hardening media.
Background technology
In order to improve the performance of the metal materials such as such as steel, need the workpiece to metal material to carry out heat treatment, conventional Technology for Heating Processing have quenching, be tempered, anneal, the heat treatment method such as normalizing.Wherein, the quenching of steel is that steel is heated to critical temperature Ac3 (sub-eutectoid steel) or Ac1 (hypereutectoid steel) temperatures above, insulation a period of time, it is allowed to all or part of austenitizing, then carries out the Technology for Heating Processing that martensite (or bainite) changes being as cold as below Ms (or isothermal near Ms) soon more than the cooling rate of critical cooling rate.During quenching, the cooling procedure of workpiece is generally divided into three phases, i.e. metal material is quenched the first stage (steam blanket stage) of steam encirclement of medium, vapor film breakage seethes with excitement second stage (boiling stage), the temperature of metal material reach the boiling point of hardening media and capture the phase III (convection current stage) of heat below by way of convection current, are then cooled to room temperature.Generally also the solution treatment of the materials such as aluminium alloy, copper alloy, titanium alloy, safety glass or the Technology for Heating Processing with quick cooling procedure are referred to as quenching.After quenching, the performance such as the intensity of steel, hardness, wearability, fatigue strength and toughness is greatly improved, thus meets various machine components and the different of instrument use requirements.Special physics, the chemical properties such as the ferromagnetism of some special steel material, corrosion resistance can also be met by quenching.
At present, conventional hardening media has water-based quenching agent and oiliness quenching medium, the feature of water-based quenching agent is all to have the highest rate of cooling in whole cooling procedure, can promote to form the workpiece that crystal grain is tiny in the rate of cooling that the high temperature cooling stage is high, be conducive to improving the performance that workpiece is final, but at cold stage, too fast rate of cooling makes the internal stress of workpiece excessive, therefore it is easily caused workpiece cracking.Compared with water-based quenching agent, the feature of oiliness quenching medium is that the rate of cooling of whole cooling stage is slow, although be possible to prevent workpiece cold stage due to internal stress excessive and cause cracking, but owing to hot stage rate of cooling is slower, therefore it is easily caused workpiece crystal grain relatively big, reduces the performance after workpiece quenching.Additionally, traditional oiliness quenching medium generally oil based on the mineral oil with petroleum distillate, it is equipped with additive and forms.The distinctive performance of mineral oil determines and can produce substantial amounts of smog when quenching, the most easily pollutes environment, and environment-friendly function is poor.And, the oiliness quenching medium rate of cooling narrow range based on mineral oil, mineral oil flash is low, easy initiation fire, uses dangerous.The rolled steel dosage and the specification that are applied to the field such as building trade, science of bridge building are continuously increased.But steel are easy rust corrosion in the surrounding mediums such as carbon dioxide, oxygen gas and water, acid during storing, transporting and use.Corrosion not only causes the waste of steel, affects the outward appearance of steel, and can cause and produce and the potential safety hazard of life.
It is thus desirable to by the formula improving existing hardening media so that it is steel workpiece excellent in mechanical performance can not only be made, and can effectively suppress the corrosion of steel workpiece.
Summary 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%；Saponifier: 0.01-5%；Import quenching auxiliary agent: 0.01-5%；Water: surplus.
Being preferably carried out mode as the present invention, by percentage to the quality, described saponifier 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 mode as the present invention, it is characterized in that, described nonionic surfactant is any one or the mixture of more than two kinds in the fatty alcohol-polyoxyethylene ether selected from C12-C18, C12-C14 alkyl polyglucoside, C12-C18 alcohol and the condensation substance of ethylene oxide/propylene oxide block copolymer, C8-C20 branched-chain alcoho polyoxyethylene ether；Described anion surfactant is for be selected from: any one or the mixture of more than two kinds in C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonate, C12-C18 alkyl alkoxy sulfate, α-sodium olefin sulfonate, C14-C18 MES.
Being preferably carried out mode as the present invention, described nonionic surfactant is spermol polyoxyethylene ether-20 or polyoxyethylene lauryl ether-10, and described anion surfactant is dodecylbenzene sodium sulfonate or Cortex cocois radicis acyl methyl taurine sodium.
Being preferably carried out mode as the present invention, described wandering agent is any one or the combination of more than two kinds in sodium aluminosilicate, sodium silicate, montmorillonite, silicon dioxide.
Being preferably carried out mode as the present invention, described wandering agent is the combination mixture of sodium silicate and sodium-based montmorillonite.
Being preferably carried out mode as the present invention, described import quenching auxiliary agent includes carboxymethyl cellulose, molybdate, carbonate, orthophosphate, nitrite, tungstates, benzoate, indole hydrochlorate, citrate and alginate.
Being preferably carried out mode as the present invention, described import quenching auxiliary agent is any one or the combination of more than two kinds in carboxymethyl cellulose, sodium molybdate, sodium carbonate, ammonium tungstate, sodium benzoate, indolebutyric acid sodium, sodium citrate and sodium alginate.
Being preferably carried out mode as the present invention, by percentage to the quality, described 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 the application in metal heat treatmet field of a kind of any one hardening media recited above.
Hardening media of the present invention has a higher rate of cooling at hot stage, about 338 DEG C/s；Relatively slow in cold stage rate of cooling, about 102 DEG C/s, this can prevent too fast cooling, contribute to crystal grain thinning, it is to avoid workpiece ftractures；Additionally there is the salt fog resistance of excellence.So the hardening media that the present invention provides has, composition is simple, be prone to preparation, low toxic and environment-friendly, low cost, easily operated and inhibition efficiency advantages of higher.
Detailed description of the invention
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication being generally understood that with one skilled in the art of the present invention.When there is contradiction, it is as the criterion with the definition in this specification.
Participate in the election of the detailed description being preferable to carry out method of the invention below and the embodiment that includes can be more easily understood present disclosure.Term used herein " comprises ", " including ", " having ", " containing " or its other deformation any, it is intended that cover the including of non-exclusionism.Such as, comprise the compositions of listed elements, step, method, goods or device and be not necessarily solely those key elements, but other not expressly listed key element or the intrinsic key element of this kind of compositions, step, method, goods or device can be included.
During the Range Representation that temperature, time or other value or parameter limit with scope, preferred scope or a series of upper limit preferred value and lower preferable values, this is appreciated that and specifically discloses all scopes formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, regardless of whether whether this scope separately discloses.Such as, when disclosing scope " 1-5 ", described scope should be interpreted as including scope " 1-4 ", " 1-3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc..When numerical range is described in this article, unless otherwise indicated, otherwise this scope is intended to include its end value and all integers within the range and mark.In the case of the most conflicting, the feature of different embodiments, embodiment or the example described in this specification and different embodiments, embodiment or example can be combined and combine by those skilled in the art.
In the description of this specification, the description of reference term " is preferably carried out scheme ", " some are preferably carried out scheme ", " as preferably scheme ", " example " or " some examples " etc. means that the specific features, structure, material or the feature that combine this embodiment or example description are contained at least one embodiment or the example of the present invention.In this manual, the schematic representation of above-mentioned term is necessarily directed to identical embodiment or example.And, the specific features of description, structure, material or feature can be to combine in one or more embodiments in office or example in an appropriate manner.Additionally, in the case of the most conflicting, the feature of the different embodiments described in this specification or example and different embodiment or example can be combined and combine by those skilled in the art.
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%；
Saponifier: 0.01-5%；
Import quenching auxiliary agent: 0.01-5%；
Water: surplus.
Zinc chloride:
Described zinc chloride is one of main functional component of hardening media of the present invention, is one of the staple product of inorganic chemicals industry, and its range of application is the widest.Zinc chloride is white particulate, bar-shaped or powder.Odorlessness.Soluble in water, it is that in solid salt, dissolubility is maximum (25 ° of C, 333g/100g), its reason is dissolved in water and forms complex acid H [ZnCl2(OH)].It is dissolved in methanol, ethanol, glycerol, acetone, ether, insoluble in liquefied ammonia.Hygroscopy is strong, can absorb moisture and deliquescence in air.There is dissolving metal-oxide and the characteristic of cellulose.Melted zinc chloride has good electric conductivity.Dense white cigarette is had to generate time scorching hot.Described zinc chloride can be prepared by crystallization after zinc or zinc oxide and hydrochloric acid reaction.
Sodium hydroxide:
Described sodium hydroxide is one of main functional component of hardening media of the present invention, chemical formula is NaOH, it is commonly called as Caustic soda, Caustic soda, caustic soda, for a kind of highly basic with severe corrosive, generally lamellar or particle shape, soluble in water, heat release when being dissolved in water, and form alkaline solution, separately there is hygroscopy, easily draw the steam generation deliquescence in air and carbon dioxide occurs rotten, hydrochloric acid can be added and check whether to go bad.Sterling is water white crystal.Density 2.130g/cm.Fusing point 318.4 DEG C.Boiling point 1390 DEG C.Industrial goods contain a small amount of sodium chloride and sodium carbonate, are the crystal of White-opalescent.There is a bulk, lamellar, granular and bar-shaped etc..
Sodium hydroxide can will be completely dissociated into the CO in sodium ion and hydroxide ion, with air in water2Reaction generates sodium carbonate, reacts with zinc chloride and can generate sodium chloride and zinc hydroxide, and zinc hydroxide is dissolved in again sodium hydroxide and obtains Zinc sodium oxide (Na2ZnO2). and water.
Saponifier:
Saponifier of the present invention contains following components: nonionic surfactant: 3-5%；Anion surfactant: 4.5-10%；Wandering agent: 4-8%；Anhydrous sodium sulfate: surplus.
Described nonionic surfactant mainly includes polyoxyethylene-type, polyol type, alkylolamides type.
Described anion surfactant is to play the surfactant that the part of surface-active action is electronegative in water after ionization, from structure, anion surfactant is divided into soap, sulfonate, sulfuric acid and the big class of phosphate ester salt four.
Described wandering agent is soluble in water, for ecru mastic or white powder, can prevent powdery paints from luming.
Described anhydrous sodium sulfate is monoclinic system, crystal short cylinder, and aggregation is compact massive or cot shape etc., and water white transparency carries pale yellow or green sometimes, soluble in water.White, odorless, the crystallization having bitterness or powder, have hygroscopicity.Profile is colourless, transparent, big crystallization or the little crystallization of graininess.It is exposed in air easily moisture absorption and becomes aqueous sulfuric acid sodium.
In the present invention is preferably carried out mode, the described nonionic surfactant any one or the mixture of more than two kinds in the fatty alcohol-polyoxyethylene ether of C12-C18, C12-C14 alkyl polyglucoside, C12-C18 alcohol and the condensation substance of ethylene oxide/propylene oxide block copolymer, C8-C20 branched-chain alcoho polyoxyethylene ether.
In the present invention is preferably carried out mode, described nonionic surfactant is selected from cetearyl alcohol polyoxyethylenated alcohol-6, ceteareth-12, ceteareth-20, cetearyl alcohol polyoxyethylenated alcohol-25, spermol polyoxyethylene ether-10, spermol polyoxyethylene ether-20, lauryl alcohol gathers, oxygen vinyl Ether-4, polyoxyethylene lauryl ether-5, polyoxyethylene lauryl ether-9, polyoxyethylene lauryl ether-10, polyoxyethylene lauryl ether-12, polyoxyethylene lauryl ether-15, polyoxyethylene lauryl ether-20, polyoxyethylene lauryl ether-23, oleic alcohol polyoxyethylene ether-10, oleic alcohol polyoxyethylene ether-20, Brij-721-10, Brij-721-20, Brij-721-100；Any one or a few mixing in cocamidopropyl propyl amide hydroxyl sulphonic acid betaine, cocoamidopropyl dimethyl glycine betaine.
In the present invention is preferably carried out mode, described anion surfactant is to be selected from: any one or the mixture of more than two kinds in C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonate, C12-C18 alkyl alkoxy sulfate, α-sodium olefin sulfonate, C14-C18 MES.
In the present invention is preferably carried out mode, described anion surfactant is selected from: any one or a few the mixing in dodecylbenzene sodium sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, fatty alcohol sodium isethionate, polyxyethylated allyl phenyl ether sulfuric acid, amide groups polyoxyethylene ether magnesium sulfate, 1-isobutyl-3,5-dimethylhexylphosphoric acid potassium salt, Dodecyl Polyoxyethylene Ether sulfosuccinate disodium, α-sodium olefin sulfonate, Cortex cocois radicis acyl methyl taurine sodium.
In the present invention is preferably carried out mode, the described wandering agent any one or the combination of more than two kinds in sodium aluminosilicate, sodium silicate, montmorillonite, the silicon dioxide.
Described wandering agent is all pressed powder state, and the mean diameter of powder is less than 10 microns.
In the present invention is preferably carried out mode, described wandering agent is the compositions of sodium silicate and sodium-based montmorillonite, and the mass ratio of described sodium silicate and sodium-based montmorillonite is 2:1.
In the present invention is preferably carried out mode, by percentage to the quality, described saponifier contains following components: nonionic surfactant: 3-5%；Anion surfactant: 4.5-10%；Wandering agent: 4-8%；Anhydrous sodium sulfate: surplus.
In the present invention is preferably carried out mode, by percentage to the quality, described saponifier contains following components: nonionic surfactant: 3-5%；Anion surfactant: 6-8%；Wandering agent: 5-7%；Anhydrous sodium sulfate: surplus.
In the present invention is preferably carried out mode, described nonionic surfactant is spermol polyoxyethylene ether-20 or polyoxyethylene lauryl ether-10, and described anion surfactant is dodecylbenzene sodium sulfonate or Cortex cocois radicis acyl methyl taurine sodium.
In the present invention is preferably carried out mode, saponifier of the present invention is prepared via a method which to obtain:
(1) adding anion surfactant and the anhydrous sodium sulfate of formula ratio in 65-70 DEG C of deionized water, stir, the pH value regulating mixed slurry with citric acid or ammonia is 7.5-8.5, it is thus achieved that mixed slurry；
(2) filter after described mixed slurry is displayed 5-10h, obtain saponifier original washing powder by being spray-dried；
(3) saponifier original washing powder is uniformly mixed with nonionic surfactant, wandering agent, i.e. obtains saponifier.
Wherein, the quality solid content of described mixed slurry controls in the range of 65-70%, and the temperature of described mixed slurry controls in the range of 65-70 DEG C.
Import quenching auxiliary agent:
Import of the present invention quenching auxiliary agent includes carboxymethyl cellulose, molybdate, carbonate, orthophosphate, nitrite, tungstates, benzoate, indole hydrochlorate, citrate and alginate.
Described carboxymethyl cellulose, also known as sodium carboxymethyl cellulose, is called for short CMC, is the cellulose kind that in the world today, range is the widest, consumption is maximum.By the cellulose derivative of carboxymethyl substituent, form alkali cellulose with naoh treatment cellulose, then react prepared with monochloroacetic acid.Sodium carboxymethyl cellulose (CMC) belongs to anionic cellulose ethers, and outward appearance is white or slightly yellow wadding fibrous powder or white powder, and odorless, tasteless is nontoxic；It is soluble in cold water or hot water, forms the clear solution with certain viscosity.Solution is neutral or alkalescence, insoluble in ethanol, ether, isopropanol, acetone and other organic solvent, dissolves in ethanol or the acetone soln of aqueous 60%.
Described molybdate includes sodium molybdate and/or calcium molybdate；Described carbonate includes sodium carbonate and/or calcium carbonate；Described orthophosphate includes ammonium phosphate and/or sodium phosphate；Described nitrite is sodium nitrite；Described tungstates includes sodium tungstate and/or artificial schellite；Described benzoate is sodium benzoate；Described indole hydrochlorate includes heteroauxing sodium, indolepopionic acid sodium, indolebutyric acid sodium and/or butyric acid potassium；Described citrate is sodium citrate；Described alginate is sodium alginate.
In the present invention is preferably carried out mode, described import quenching auxiliary agent is any one or the combination of more than two kinds in carboxymethyl cellulose, sodium molybdate, sodium carbonate, sodium benzoate, indolebutyric acid sodium, sodium citrate.
In the present invention is preferably carried out mode, by percentage to the quality, described import quenching auxiliary agent contains following components: carboxymethyl cellulose: 20-60%；Sodium molybdate: 1-15%；Sodium carbonate: 1-15%；Indolebutyric acid sodium: 50-70%.
In the present invention is preferably carried out mode, by percentage to the quality, described 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 preparing described hardening media, it comprises the steps of:
(1) by component bigger for granule in formula through crushing, grind and sieving, powder is made；
(2) in the water of formula ratio, above-mentioned dusty raw materials and other component raw material, mix homogeneously are added while stirring.
After red-hot workpiece enters hardening media of the present invention, the high-temperature region of 650～500 DEG C, water around surface of the work is heated rapidly, vaporizes formation steam blanket, because steam is the non-conductor of heat, it constrains the water performance in high-temperature region cooling capacity, therefore the rate of cooling of workpiece declines rapidly；Meanwhile, sodium salt in hardening media, zinc salt etc. separate out at surface of the work, and are heated, burst, thus tear steam blanket, and then the water in hardening media contacts with surface of the work again, re-forms steam blanket, such iterative cycles.Low-temperature space below 300 DEG C, the zinc chloride crystal that surface of the work separates out is thickened reinforcement by import quenching auxiliary agent, the deposit making surface of the work produce no longer produces explosion, and the steam blanket of formation can not be torn again, and therefore deposit adds steam blanket and serves good solid vapour Duoble heat effect.
Additionally; the discovery that the present inventor is unexpected; described saponifier coordinates import quenching auxiliary agent can effectively reduce quenching distortion and cracking; and make steel possess good corrosion resistance; speculate that possible reason is that saponifier coordinates import quenching auxiliary agent can promote that steel surface forms layer protecting film, improve the hardening media cooling stability when high temperature and rate of cooling, and also can stably slow down the rate of cooling of workpiece at cold stage; to prevent too fast cooling, thus avoid workpiece cracking.In addition the anti-corrosion component contained in import quenching auxiliary agent is except improving the corrosion resistance of metal, and can improve the stability of protecting film.
Hardening media of the present invention can apply to metal heat treatmet field, quenches steel component.
Hardening media of the present invention is applicable to carbon steel and structural alloy steel.Described structural alloy steel can be divided into common structural alloy steel and specific use structural alloy steel.The former includes Hi-Stren steel, cryogenic steel, unimach, carburizing 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 require have higher yield strength, tensile strength and fatigue strength, enough plasticity and toughness.Described structural alloy steel is widely used in the structures such as boats and ships, vehicle, aircraft, guided missile, weapons, railway, bridge, pressure vessel, lathe.Hardening media of the present invention is best suitable for processing and corrosion resistance is required higher steel, can obtain high-performance corrosion-resisting steel.Hardening media of the present invention contributes to improving the tissue morphology of corrosion-resisting steel, refines austenite structure, stops or delay carbon to separate out too early in cooling procedure so that it is diffusional precipitation in ferrite, improving its intensity.
Organizational structure in actual production, for the corrosion-resisting steel product of certain specific standard and purposes, it is necessary to reasonably determine the technological parameter of cooling procedure, needed for obtaining.The use temperature of hardening media of the present invention should control within 25～50 DEG C, can use cooling water cooling or hydronic for hardening media method is carried out temperature control.
Hardening media of the present invention has that composition is simple, be prone to preparation, low toxic and environment-friendly, low cost, easily operated and inhibition efficiency advantages of higher, has good application prospect.
Below by some embodiments and embodiment, comparative example, the present invention is explained in more detail, it should be appreciated 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%；Saponifier: 0.01-5%；Import quenching auxiliary agent: 0.01-5%；Water: surplus.
Embodiment 2, identical with embodiment 1, difference is, by percentage to the quality, described saponifier contains following components: nonionic surfactant: 3-5%；Anion surfactant: 4.5-10%；Wandering agent: 4-8%；Anhydrous sodium sulfate: surplus.
Embodiment 3, identical with embodiment 2, difference is, described nonionic surfactant is any one or the mixture of more than two kinds in the fatty alcohol-polyoxyethylene ether selected from C12-C18, C12-C14 alkyl polyglucoside, C12-C18 alcohol and the condensation substance of ethylene oxide/propylene oxide block copolymer, C8-C20 branched-chain alcoho polyoxyethylene ether；Described anion surfactant is for be selected from: any one or the mixture of more than two kinds in C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonate, C12-C18 alkyl alkoxy sulfate, α-sodium olefin sulfonate, C14-C18 MES.
Embodiment 4, identical with embodiment 2, difference is, described nonionic surfactant is spermol polyoxyethylene ether-20 or polyoxyethylene lauryl ether-10, and described anion surfactant is dodecylbenzene sodium sulfonate or Cortex cocois radicis acyl methyl taurine sodium.
Embodiment 5, identical with embodiment 2, difference is, described wandering agent is any one or the combination of more than two kinds in sodium aluminosilicate, sodium silicate, montmorillonite, silicon dioxide.
Embodiment 6, identical with embodiment 2, difference is, described wandering agent is the combination mixture of sodium silicate and sodium-based montmorillonite.
Embodiment 7, identical with embodiment 1, difference is, described import quenching auxiliary agent includes carboxymethyl cellulose, molybdate, carbonate, orthophosphate, nitrite, tungstates, benzoate, indole hydrochlorate, citrate and alginate.
Embodiment 8, identical with embodiment 1, difference is, described import quenching auxiliary agent is any one or the combination of more than two kinds in carboxymethyl cellulose, sodium molybdate, sodium carbonate, ammonium tungstate, sodium benzoate, indolebutyric acid sodium, sodium citrate and sodium alginate.
Embodiment 9, identical with embodiment 1, difference is, by percentage to the quality, described import quenching auxiliary agent contains following components: carboxymethyl cellulose: 20-60%；Sodium molybdate: 1-15%；Sodium carbonate: 1-15%；Indolebutyric acid sodium: 50-70%.
Embodiment 10, any one hardening media application in metal heat treatmet field in a kind of embodiment 1-9.
It is commercially available that the raw material that embodiment in detail below and comparative example use such as does not has specified otherwise to be, and wherein, anhydrous sodium sulfate is purchased from Shanghai hundred million rising sun Trade Co., Ltd.；Complex silicate sodium is purchased from Qingdao Dongyue Sodium Silicate Co., Ltd.；Sodium-based montmorillonite is purchased from Zhejiang Fenghong New Material Co., Ltd.；Carboxymethyl cellulose is purchased from Jinzhou City Hong Hai cellulose company limited；Indolebutyric acid sodium is purchased from Zhengzhou Yin Hai Chemical Co., Ltd., wherein:
A-1: saponifier: by percentage to the quality, it contains 4% polyoxyethylene lauryl ether-10,7% dodecylbenzene sodium sulfonate, 4% complex silicate sodium, 2% sodium-based montmorillonite and 83% anhydrous sodium sulfate；It is prepared via a method which to obtain:
(1) adding dodecylbenzene sodium sulfonate and the anhydrous sodium sulfate of formula ratio in 65 DEG C of deionized waters, stir, the pH value regulating mixed slurry with citric acid or ammonia is 8.0, it is thus achieved that quality solid content is the mixed slurry of 68 %；
(2) filter after the mixed slurry that step (1) obtains is displayed 7h, obtain saponifier original washing powder by being spray-dried；
(3) saponifier original washing powder step (2) obtained and nonionic surfactant polyoxyethylene lauryl ether-10, sodium silicate, sodium-based montmorillonite are uniformly mixed and i.e. obtain saponifier.
A-2: saponifier: by percentage to the quality, it contains 4% polyoxyethylene lauryl ether-10,7% dodecylbenzene sodium sulfonate, 6% complex silicate sodium and 83% anhydrous sodium sulfate；Preparation method is identical with A-1 saponifier, and difference is without sodium-based montmorillonite composition.
A-3: saponifier: by percentage to the quality, it contains 5% spermol polyoxyethylene ether-20,10% dodecylbenzene sodium sulfonate, 6% complex silicate sodium, 2% sodium-based montmorillonite and 77% anhydrous sodium sulfate；Preparation method is identical with A-1 saponifier, and difference is that nonionic surfactant is spermol polyoxyethylene ether-20.
B-1: import quenching auxiliary agent: by percentage to the quality, it contains: 25% carboxymethyl cellulose；5% sodium molybdate；10% sodium carbonate；60% indolebutyric acid sodium.
B-2: import quenching auxiliary agent: by percentage to the quality, it contains: 55% carboxymethyl cellulose；5% sodium molybdate；10% sodium carbonate；30% indolebutyric acid sodium.
B-3: import quenching auxiliary agent: by percentage to the quality, it contains: 85% carboxymethyl cellulose；5% sodium molybdate；10% sodium carbonate.
B-4: import quenching auxiliary agent: by percentage to the quality, it contains: 25% carboxymethyl cellulose；5% ammonium tungstate；10% sodium carbonate；30% sodium benzoate；30% sodium citrate.
Example 1 below-10 and the preparation method of comparative example 1-5 hardening media, comprise the steps of:
(1) by component bigger for granule in formula through crushing, grind and sieving, powder is made；
(2) in the deionized water of formula ratio, above-mentioned dusty raw materials and other component raw material, mix homogeneously are added while stirring.
The hardening media obtaining example 1 below-10 and comparative example 1-5 carries out following test and evaluation:
(1) " material critical temperature and continuous cooling curve measuring and analysing meter " test hardening media rate of cooling under different temperatures interval using model to be ZH9667.
(2) 850 DEG C of normalizings of heat treating regime, 840 DEG C of quenchings, the condition of 600 DEG C of tempering is recommended to process according to the 45# steel of regulation in GB/T699-1999 standard, the 45# steel plate that thickness is 45mm is put in each hardening media, measure case hardness (HRC) value of steel plate sample after quenching and observe whether it has cracking phenomena, result such as table 1.
(3) its corrosion resistance will be tested after the 40Cr steel plate sample warm water that test (2) processes cleans；Prepare referring particularly to standard GB/T/T10125-1997, salt spray test solution: NaCl and distilled water.The concentration of solution is 50 ± 5 g/L, and pH value is 6.5～7.2, and the temperature inside the box is 35 ± 2 DEG C, and salt fog settling amount is 1.0～2.0 ml/80 cm2•h；Salt spray test method: steel plate sample is placed in salt fog cabinet straight at 30-45 ° of direction, spraying 24 h are a cycle continuously, respectively 1 and 2 cycle of spraying.After experiment terminates, it is placed on Indoor Natural and is dried 0.5～1 h, then clean with room temperature water, and dry up immediately, measure sample rate of corrosion, result such as table 1 with 3 mm × 3 mm grids.
Embodiment 1:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-1；3g import quenching auxiliary agent B-1；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 341.1 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 100.6 DEG C/s.
Embodiment 2:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-2；3g import quenching auxiliary agent B-1；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 340.6 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 107.3 DEG C/s.
Embodiment 3:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-3；3g import quenching auxiliary agent B-1；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 342.7 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 102.6 DEG C/s.
Embodiment 4:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-1；3g import quenching auxiliary agent B-2；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 338.8 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 110.1 DEG C/s.
Embodiment 5:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-1；3g import quenching auxiliary agent B-3；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 333.2 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 108.9 DEG C/s.
Embodiment 6:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-1；3g import quenching auxiliary agent B-4；88g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 328.4 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 112.3 DEG C/s.
Embodiment 7:
Hardening media is prepared: 7g zinc chloride according to following formula；8g sodium hydroxide；2.5g saponifier A-1；3.5g import quenching auxiliary agent B-1；79g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 343.2 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 99.8 DEG C/s.
Embodiment 8:
Hardening media is prepared: 7g zinc chloride according to following formula；8g sodium hydroxide；2.5g saponifier A-1；3.5g import quenching auxiliary agent B-2；79g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 323.7 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 109.7 DEG C/s.
Embodiment 9:
Hardening media is prepared: 7g zinc chloride according to following formula；8g sodium hydroxide；2.5g saponifier A-1；3.5g import quenching auxiliary agent B-3；79g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 330.5 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 107.2 DEG C/s.
Embodiment 10:
Hardening media is prepared: 7g zinc chloride according to following formula；8g sodium hydroxide；2.5g saponifier A-1；3.5g import quenching auxiliary agent B-4；79g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 329.6 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 108.9 DEG C/s.
Comparative example 1:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；1.5g saponifier A-1；91g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 175.4 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 88.0 DEG C/s.
Comparative example 2:
Hardening media is prepared: 3.5g zinc chloride according to following formula；4g sodium hydroxide；3g import quenching auxiliary agent B-1；89.5g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 189.2 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 90.6 DEG C/s.
Comparative example 3:
Hardening media is prepared: 10g sodium chloride according to following formula；8g potassium chloride；8g sodium nitrate；74g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 145.1 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 121.6 DEG C/s.
Comparative example 4:
Hardening media is prepared: 3g polyethers (molecular weight is 38000) according to following formula；6g isopropanolamine；1.2g sodium molybdate；0.5g fluorine silicon defoaming agent；89.3g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 176.5 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 105.6 DEG C/s.
Comparative example 5:
Hardening media is prepared: 45g polyethers (molecular weight is 50000) according to following formula；5g isopropanolamine；1g sodium molybdate；1.2g fluorine silicon defoaming agent；47.8g deionized water.
Recording through test, the hardening media that the present embodiment provides high-temperature region more than 400 DEG C, maximum rate of cooling is 132.2 DEG C/s, and the low-temperature space below 400 DEG C, the fastest rate of cooling is 95.4 DEG C/s.
Table 1
From rate of cooling and the above-mentioned data of hardening media, in comparative example, hardening media is relatively slow in the rate of cooling of hot stage, relatively accelerates in cold stage rate of cooling.And embodiment of the present invention hardening media has higher rate of cooling at hot stage, about 338 DEG C/s；And relatively slow in cold stage rate of cooling, about 102 DEG C/s, cool time extends, and effectively prevents too fast cooling, contributes to crystal grain thinning, thus avoids workpiece cracking.Compared with comparative example, embodiment of the present invention hardening media also has more preferable salt fog resistance.
Aforesaid example is merely illustrative, for explaining some features of the feature of the disclosure.Appended claim is intended to the widest scope that requirement it is contemplated that, and embodiments as presented herein is only the explanation of embodiment of selection of combination according to all possible embodiment.Therefore, the purpose of applicant is that appended claim is not by the selectional restriction of the example of explanation inventive feature.And the progress in science and technology will form the possible equivalent not being presently considered due to the inaccurate reason of language performance or son replacement, and these changes also should be interpreted to be covered by appended claim in the conceived case.
Claims (10)
1. a hardening media, it is characterised in that by percentage to the quality, it contains following components:
Zinc chloride: 0.5-10%；
Sodium hydroxide: 1-15%；
Saponifier: 0.01-5%；
Import quenching auxiliary agent: 0.01-5%；
Water: surplus.
Hardening media the most according to claim 1, it is characterised in that by percentage to the quality, described saponifier contains following components: nonionic surfactant: 3-5%；Anion surfactant: 4.5-10%；Wandering agent: 4-8%；Anhydrous sodium sulfate: surplus.
Hardening media the most according to claim 2, it is characterized in that, described nonionic surfactant is any one or the mixture of more than two kinds in the fatty alcohol-polyoxyethylene ether selected from C12-C18, C12-C14 alkyl polyglucoside, C12-C18 alcohol and the condensation substance of ethylene oxide/propylene oxide block copolymer, C8-C20 branched-chain alcoho polyoxyethylene ether；Described anion surfactant is for be selected from: any one or the mixture of more than two kinds in C12-C18 fatty acid soaps, C11-C18 alkylbenzenesulfonate, C12-C18 alkyl alkoxy sulfate, α-sodium olefin sulfonate, C14-C18 MES.
Hardening media the most according to claim 2; it is characterized in that; described nonionic surfactant is spermol polyoxyethylene ether-20 or polyoxyethylene lauryl ether-10, and described anion surfactant is dodecylbenzene sodium sulfonate or Cortex cocois radicis acyl methyl taurine sodium.
Hardening media the most according to claim 2, it is characterised in that described wandering agent is any one or the combination of more than two kinds in sodium aluminosilicate, sodium silicate, montmorillonite, silicon dioxide.
Hardening media the most according to claim 5, it is characterised in that described wandering agent is the combination mixture of sodium silicate and sodium-based montmorillonite.
Hardening media the most according to claim 1, it is characterised in that described import quenching auxiliary agent includes carboxymethyl cellulose, molybdate, carbonate, orthophosphate, nitrite, tungstates, benzoate, indole hydrochlorate, citrate and alginate.
Hardening media the most according to claim 1, it is characterized in that, described import quenching auxiliary agent is any one or the combination of more than two kinds in carboxymethyl cellulose, sodium molybdate, sodium carbonate, ammonium tungstate, sodium benzoate, indolebutyric acid sodium, sodium citrate and sodium alginate.
Hardening media the most according to claim 1, it is characterised in that by percentage to the quality, described import quenching auxiliary agent contains following components: carboxymethyl cellulose: 20-60%；Sodium molybdate: 1-15%；Sodium carbonate: 1-15%；Indolebutyric acid sodium: 50-70%.
10. the application in metal heat treatmet field of the hardening media described in claim 1-9 any one.
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| CN107190125A (en) * | 2017-06-15 | 2017-09-22 | 上海金兆节能科技有限公司 | A kind of environmentally friendly quenching liquid and preparation method thereof |
| 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 |
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| CN111334650A (en) * | 2020-04-01 | 2020-06-26 | 南宁学院 | Metal tool quenching liquid |
| CN113512680A (en) * | 2021-06-21 | 2021-10-19 | 中联重科股份有限公司 | Concrete conveying pipe, preparation method thereof and concrete pump truck |
| CN118122965A (en) * | 2024-04-22 | 2024-06-04 | 无锡市法兰锻造有限公司 | Technological method for improving hardenability of 09MnNiD low-temperature steel forging |
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| CN118122965A (en) * | 2024-04-22 | 2024-06-04 | 无锡市法兰锻造有限公司 | Technological method for improving hardenability of 09MnNiD low-temperature steel forging |
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