CN105624448B - Melting cast aluminum alloy flux of deslagging refining containing rare earth and preparation method thereof - Google Patents
Melting cast aluminum alloy flux of deslagging refining containing rare earth and preparation method thereof Download PDFInfo
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- CN105624448B CN105624448B CN201610184371.9A CN201610184371A CN105624448B CN 105624448 B CN105624448 B CN 105624448B CN 201610184371 A CN201610184371 A CN 201610184371A CN 105624448 B CN105624448 B CN 105624448B
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The present invention is a kind of melting cast aluminum alloy deslagging refining flux and preparation method thereof.The flux is added with sodium chloride by by the rare earth oxide of fine-powdered and rare earth carbonate, and potassium chloride, cryolite, prodan, sodium carbonate during calcirm-fluoride is for the powder of main body, is made after agitated, dehydration and curing.Based on rare earth is to the metamorphism of aluminium alloy, passivation and promotes a series of low-melting impurities to form the characteristics such as infusible compounds, can effective purifying aluminum alloy liquid using the flux in melting, improve mobility and casting character, promote the refinement and second of crystal grain in aluminium alloy cast sturcture in transgranular disperse educt, so as to be favorably improved the intensity of aluminium alloy, hardness, wearability and corrosion resistance.The drawbacks of flux effectively overcomes existing aluminium alloy deslagging refining flux a large amount of toxic and harmfuls and flue dust is produced during purified treatment aluminum alloy melt.
Description
Technical field
The present invention relates to the deslagging refining flux that purifying aluminum alloy liquation during a kind of melting cast aluminum alloy is used
And preparation method thereof.
Background technology
The fusion process of cast aluminium alloy gold is divided into fusing, adjusts composition, and deslagging refining, Metamorphism treatment adjusts temperature and pours
Note.Because furnace charge is unclean, the oxidation of furnace charge generating surface, cause to exist inside the aluminum alloy melt for having melted it is a number of be mingled with and
Gas, has by metal oxide on liquid level and is involved in scum silica frost or slag that exogenous impurity mixture is constituted.This scum silica frost and point
Being dispersed in being mingled with liquation must eliminate with gas, to ensure the pure of cast structure.Therefore, deslagging refining is necessary purification
Handling process.It is general to use 1) flux to process, including such as carbon trichloride treatment of volatility flux, and fixedness flux is as being fluorinated
The treatment such as calcium.2) inert gas blowing.3) filter.Or using the treatment of above method combined purifying.Most widely used at present is also most
Economic basic handling method is flux facture.I.e. after after alloy melting with bell jar be pressed into account for quality of furnace charge fraction 0.2%-
0.5% with sodium chloride, potassium chloride as main body and contain above-mentioned single or multiple components aluminium alloy deslagging refining agent.Above-mentioned place
Although reason process can to varying degrees remove the oxide and intermetallic of the gas and 40%-80% in aluminum alloy melt
Thing, but volume of smoke and the poisonous gas that is corrosive also are produced simultaneously, deteriorate operating environment, increase alloy melting loss rate, it is difficult to
Obtain dense structure, the aluminum alloy materials without slag, bubble-free and field trash.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of cast aluminium alloy gold deslagging refining flux, to solve existing skill
Above mentioned problem present in art, cast aluminium alloy gold liquation is carried out with this flux composition of the invention ought at deslagging refining
Smoke dust and pernicious gas, can effective purifying aluminum alloy liquid, mobility and casting character are improved, in promoting aluminium alloy cast sturcture
The refinement of crystal grain and second is in transgranular disperse educt, so that the intensity of aluminium alloy, hardness, wearability and corrosion resistance are improved,
Alloy melting loss rate is reduced simultaneously.
It is a further object to provide a kind of preparation method of above-mentioned composition.
Technical scheme：Melting cast aluminum alloy of the invention deslagging refining flux composition, count by weight percentage
Composition be：
Wherein：
Preferably, weight content of the described rare earth oxide in melting cast aluminum alloy deslagging refining flux is
0.6%-1.5%, weight content of the rare earth carbonate in melting cast aluminum alloy deslagging refining flux is 1.0%-
1.8%.
The rare earth oxide is lanthana, cerium oxide or praseodymium oxide, or three kinds of combinations of oxide；Rare earth carbonate
It is cerous carbonate or lanthanum carbonate.
When described rare earth oxide is lanthana, cerium oxide, the combination of three kinds of oxides of praseodymium oxide, its composition is with weight
It is calculated as：
The content of lanthana is 25%-35%,
The content of cerium oxide is 60%-70%,
The content of praseodymium oxide is 2%-5%.
When described rare earth carbonate is the combination of cerous carbonate and lanthanum carbonate, composition by weight is：
The content of cerous carbonate is 70%-80%,
The content of lanthanum carbonate is 20%-30%.
The granularity of the RE oxide powder is 2-5 μm.
The granularity of the rare earth carbonate powder is 5-8 μm.
The preparation method of melting cast aluminum alloy deslagging refining flux of the invention is comprised the following steps：
A) temperature and normal pressure by sodium chloride, potassium chloride, cryolite, prodan and calcirm-fluoride at 100 DEG C -135 DEG C
Lower to mix 45 minutes, formation uniformly dries powder mixture；
B) to adding sodium carbonate, rare earth oxide and rare earth carbonate in the mixture, in 90 DEG C -115 DEG C of temperature and
Mixed 30 minutes under normal pressure；
C) natural cooling is stirred 20 minutes.
Flux composition of the invention can carry out slagging-off essence to cast aluminium alloy gold liquation using conventional solvent handling process
Refining.For example, to aluminium diecasting alloy, (alloy designations are different, then locate when aluminium alloy temperature reaches the treatment temperature of technological requirement
Reason temperature is different, and treatment temperature is conducive to scarfing cinder and refining higher than 50 DEG C -80 DEG C of corresponding trade mark pouring temperature), by flux basin
In shape bell jar press-in aluminium alloy, (about 10 centimetres from furnace bottom) move in a circle, to allow powder everywhere and by bell jar in translation stove
Dispersed precipitate is in bath as far as possible, to accelerate reaction speed.Such as used in smelting furnace is concentrated, then most preferably use the dress that dusts
Put, with the inert gas suction and conveying flux powder, complete to mix and blow purified treatment.Dust about 10-15 minutes time, make its disperse as far as possible
Bath is distributed in, to ensure that reaction is complete.Addition can be adjusted suitably depending on the ratio of impurity content in alloy and foundry returns,
Then about 5-10 minutes minute is stood, until slag liquid is completely separated, untill slag powdering, cast of finally skimming.
Beneficial effect：In above-mentioned flux composition, rare earth oxide and rare earth carbonate after aluminium liquid is added, by group
Divide cryolite and prodan localized hyperthermia's fluctuation of energy that exothermic reaction is formed under aluminum alloy melt smelting temperature, by alloy
Aluminium element in liquid is directly reduced to the rare earth element with fresh activity surface, and the atomic state activity that the activity of precipitation is very big is dilute
Native [RE], the hydride (680--750C) stable with hydrogen generation in aluminium melting temperature range：[RE]+2 [H]=[REH2].This
Reaction system exothermic reaction, with temperature drop, the hydride is all the more stablized, so as to reach the purpose of solid hydrogen and dehydrogenation.This method is complete
Bubble is produced in aluminium liquid by flux different from conventional, with bubble as carrier, was floated in aluminum alloy melt using bubble
Ambient gas are adsorbed in journey, to reach the purpose of dehydrogenation degasification.Using the chemical property that rare earth element is active, can be with aluminum alloy melt
In oxygen, nitrogen, the impurity such as hydrogen and a series of low-melting impurities form fusing point infusible compound high respectively, it is easy to and slag one
Rise and excluded from molten metal, reach the purpose of deslagging refining.
Using rare earth element to the affinity of oxygen more than aluminium and the affinity of oxygen, therefore [RE] can be restored from oxide inclusion
Aluminium, reduces alumina inclusion.
Using rare-earth flux two-layer diaphragm is produced in aluminium liquid purification：Internal layer：Fine and close protection is woven into by fibre strip
Network, it is adsorbable to be mingled with and flux and the reaction product matter being mingled with, it is ensured that the purification of aluminium liquid.The outer layer of ingress of air：By
Crystalline state material is constituted, and serves the effect of isolation air conservation aluminium liquid.
Using rare-earth flux to the refining effect of aluminum alloy melt, the mobility and casting character of aluminum alloy melt can be improved,
Refining alloy cast sturcture, act as different with aluminium and some alloying elements or impurity (Fe, Si, S etc.) formation high melting compound
Matter nucleus, or separated out in crystal boundary, prevent crystal grain to grow up due to pinning effect.Rare earth surface-active is high, can reduce nucleus table
Face energy, increases crystallization nucleation rate.Rare earth is extremely low in aluminium liquid solid solubility, and metal surface activity class material, easily in crystal boundary and boundary
Upper absorption segregation, the defect filled up on interface, so as to hinder the growth of crystal, eliminates the continuous net being distributed along crystal boundary in aluminium alloy
Shape structure, makes alloy strength, and hardness, wearability and corrosion resistance are improved.
The bubble that decomposition reaction is discharged at a temperature of aluminium alloy smelting using sodium carbonate, can effectively adsorb molten aluminium alloy
The gas of middle dissolving and the tiny particle of Dispersed precipitate.The sodium chloride for putting into according to a certain ratio, potassium chloride and calcirm-fluoride, close in aluminium
Under golden smelting temperature formed low melting point and easily catch impurity simultaneously with the non-wetted flux of aluminum alloy melt, be conducive to slag making and slag
Aluminium is separated.The combination of these components and the above-mentioned percentage range of each component, are determined by lot of experiments, combinations thereof
And percentage range makes cast aluminium alloy gold deslagging refining flux composition of the present invention have above-mentioned purified treatment effect, alloy is comprehensive
Close performance and the environmentally friendly excellent balance without noxious fume.
Whole processing procedure smoke dust and pungent toxic and harmful disengage, aluminium alloy content in the waste residue collected after treatment
Percentage by weight is not higher than 5%.The mobility of aluminum alloy melt is improved, and structure property improves.
Specific embodiment
The present invention is further illustrated below by embodiment and comparative example.Following examples and comparative example, mainly in China
The engineering and technological research institute Materials Research Laboratories and its research and development car of automobile aluminum wheel hub production base -- CITIC Dicastal Co., Ltd.
Between the melting Ministry of worker, be that supporting bright qi (Yizheng) aluminium alloy smelting Ministry of worker of aluminium wheels Co., Ltd of Volkswagen and Zhuhai City are high
The Die Casting Workshop production scene of new spectra Run Xingtai Electrical Appliances Co., Ltd completes.In high spot reviews process of the test produce smell,
Cigarette, slag aluminium is separated, the color and clean-up effect of slag.Experiment first determines the work processed required by flux of the flux and routine
Skill condition is consistent, be can be used in 700-780 DEG C of temperature range；Additional proportion can be adjusted between 0.2wt%-0.4wt%
Section.On this basis, when selection pouring temperature is 700 DEG C, cast punching block casting rod sample, sprue bush die sample and mobility sample
Product.K moulds sampling observation the amount of inclusions, grain size, pinhole rate, while carrying out microstructure observation, are removed the gred smart with comprehensive descision
The effect of refining.
Example 1：
Example 2
Example 3
Described rare earth oxide is lanthana, cerium oxide or praseodymium oxide, or is three kinds of compositions of oxide：
The weight content of lanthana is 25%-35%,
The weight content of cerium oxide is 60%-70%,
The weight content of praseodymium oxide is 2%-5%.
Described rare earth carbonate is cerous carbonate or lanthanum carbonate.
The weight content of cerous carbonate is 70%-80%,
The weight content of lanthanum carbonate is 20%-30%.
Embodiment 1
It is molten using the special deslagging refining of aluminium alloy containing carbon trichloride in the reverberatory furnace that cast aluminium alloy gold capacity is 10 tons
Agent, addition is the 0.2% of aluminium alloy weight, i.e., 20 kilograms.Operating procedure is as previously described.When the flux enters aluminium alloy liquid level
Hereinafter, produced in ullage immediately and volume of smoke and extend to whole workshop rapidly, and have sharp aroma.Float on liquid level
Slag is thick, and accompanies 30% or so aluminium alloy.It is poor that aluminum alloy melt not exclusively shows mobility because of purification.Fracture
Crystal grain is thicker and can be clearly visible slag inclusion and stain.
Comparative example 1
In smelting equipment similarly to Example 1, under conditions of same operating mode trade mark cast aluminium alloy gold identical with melting, make
Flux of the invention is used, addition is the 0.2% of aluminium alloy weight, i.e., 20 kilograms, operating procedure is with embodiment 1.Melted when this
Below agent press-in aluminium alloy liquid level, ullage can constantly emerge bubble, but without flue dust and sharp aroma, finally float over liquid level
On slag be powdery, it is easy to claw, 5% or so aluminium alloy accompanied in waste residue.Aluminum alloy melt shows completely because of purification
Good mobility.Fracture crystal grain is thinner, not existing slag inclusion.
Embodiment 2
In the Die Casting Workshop that aluminium alloy capacity is 10 tons concentrates smelting furnace, sodium chloride-containing, potassium chloride and ice crystal are used
The special deslagging refining agent of aluminium alloy of component, addition is the 0.25% of aluminium alloy weight, i.e., 25 kilograms.The aluminium alloy in molten bath
When the temperature of liquid is higher than 80 DEG C of pouring temperature, with blowing process, apart from the centimeters of molten bath bottom 10 by 25 kilograms of flux with
Nitrogen stream is sprayed into molten aluminium alloy, a large amount of bubbles is produced in ullage immediately, while having volume of smoke and extending to rapidly
Whole workshop, and have sharp aroma.In about 10 minutes reaction time, after completion of the reaction, 6 minutes are stood, carry out taking off Slag treatment.Slag
Quantity is larger, more sticky, and 20% or so aluminium alloy is accompanied in slag.Aluminum alloy melt mobility is preferable.Crystal grain normally meets the requirements,
Have no slag inclusion.
Comparative example 2
Under conditions of the grade aluminium alloy identical with melting of operating mode similarly to Example 2, using flux of the invention, plus
It is the 0.25% of aluminium alloy weight to enter amount, i.e., 25 kilograms, operating procedure is with embodiment 2.When flux nitrogen stream suction and conveying pressure
Enter when below aluminium alloy liquid level, ullage can constantly emerge a large amount of bubbles, but without flue dust and sharp aroma, PROCESS FOR TREATMENT is complete
Finish, it is powdery finally to float over the slag on liquid level, it is easy to claw, 5% or so aluminium alloy is accompanied in waste residue.Aluminum alloy melt because
Purification shows good mobility completely.Crystal grain is substantially refined, dense structure, has no slag inclusion.
Embodiment 3
In the aluminum alloy melting and holding furnace of the kg capacity of machine side 350 of High pressure casting machine, using with the composition of comparative example 1
The consistent flux of the invention of proportioning, addition is 0.2% of aluminium alloy capacity in the machine side stove, i.e., 0.7 kilogram.Operating procedure
With embodiment 1.Below flux press-in aluminium alloy liquid level, ullage can constantly emerge bubble, not have flue dust and pungent
Smell, although the slag finally floated on liquid level is still powdery, because the aluminium alloy temperature that furnace technology control in machine side is required is low
In comparative example 1 in reverberatory furnace aluminum alloy melt technological control temperature, it is general low 20-30 DEG C, caused part rare earth oxide
It is not engaged in reacting and remains in slag, slag is more sticky, and 15% or so aluminium alloy is accompanied in waste residue.Aluminum alloy melt flows
Property it is good, fracture crystal grain is thinner, not existing slag inclusion.But overall clean-up effect is not as good as comparative example 1.
Comparative example 3
Under conditions of the grade aluminium alloy identical with melting of operating mode similarly to Example 3, removed the gred using for machine side stove
Flux designed by refining treatment, cryolite and prodan addition that will be in flux of the present invention be improved to the upper limit, i.e.,
15% and 20%, the content of sodium chloride and potassium chloride is respectively reduced by 5%, other component ratios are constant.When flux press-in aluminium
Below alloy liquid level, ullage can constantly emerge bubble, not have flue dust and sharp aroma.Due to prodan and cryolite
The heat of local release increase and fluctuation of energy aggravation, be that rare earth oxide reduction at a lower temperature is created and more had
The condition of profit.The slag on liquid level is finally floated over for powdery, without rare earth oxide residual, it is easy to claw, 5% is accompanied in waste residue
The aluminium alloy of left and right.Aluminum alloy melt shows good mobility completely because of purification.Fracture crystal grain is thinner, hence it is evident that refinement, tissue
It is dense, not existing slag inclusion.
Experimental result is illustrated, no matter on environmental protection is carried out production strictly in line with rules and regulations, or on combination property is improved, casting of the invention
Make traditional deslagging refining agent that aluminium alloy deslagging refining flux composition is all markedly superior to comparative example.
Claims (8)
1. a kind of melting cast aluminum alloy deslagging refining flux, it is characterised in that flux composition count by weight percentage
For：
2. according to the deslagging refining flux of the melting cast aluminum alloy described in claim 1, it is characterised in that described rare earth oxygen
Weight content of the compound in melting cast aluminum alloy deslagging refining flux is 0.6%-1.5%, and rare earth carbonate is in casting
Weight content in aluminium alloy smelting deslagging refining flux is 1.0%-1.8%.
3. according to the cast zinc alloy melting deslagging refining flux described in claim 1, it is characterised in that the rare-earth oxidation
Thing is lanthana, cerium oxide or praseodymium oxide, or three kinds of combinations of oxide；Rare earth carbonate is cerous carbonate or lanthanum carbonate.
4. according to the deslagging refining flux of the melting cast aluminum alloy described in claim 3, it is characterised in that described rare earth oxygen
When compound is lanthana, cerium oxide, the combination of three kinds of oxides of praseodymium oxide, its composition is by weight：
The content of lanthana is 25%-35%,
The content of cerium oxide is 60%-70%,
The content of praseodymium oxide is 2%-5%.
5. according to the deslagging refining flux of the melting cast aluminum alloy described in claim 3, it is characterised in that described rare earth carbon
When hydrochlorate is the combination of cerous carbonate and lanthanum carbonate, composition by weight is：
The content of cerous carbonate is 70%-80%,
The content of lanthanum carbonate is 20%-30%.
6. according to the deslagging refining flux of the melting cast aluminum alloy described in claim 3 or 4, it is characterised in that the rare earth oxygen
The granularity of compound powder is 2-5 μm.
7. according to the deslagging refining flux of the melting cast aluminum alloy described in claim 3 or 5, it is characterised in that the rare earth carbon
The granularity of silicate powder is 5-8 μm.
8. a kind of melting cast aluminum alloy as claimed in claim 1 preparation method of deslagging refining flux, it is characterised in that
The preparation method is comprised the following steps：
A) sodium chloride, potassium chloride, cryolite, prodan and calcirm-fluoride are mixed at 100 DEG C -135 DEG C of temperature and normal pressure
Stirring 45 minutes is closed, formation uniformly dries powder mixture；
B) to addition sodium carbonate, rare earth oxide and rare earth carbonate, temperature and normal pressure at 90 DEG C -115 DEG C in the mixture
It is lower to mix 30 minutes；
C) natural cooling is stirred 20 minutes.
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| CN106756143B (en) * | 2017-01-04 | 2018-12-21 | 山东南山铝业股份有限公司 | Aluminium and aluminium alloy melt refining flux and aluminium and aluminium alloy melt method of refining |
| CN108118196A (en) * | 2017-12-15 | 2018-06-05 | 南通昂申金属材料有限公司 | A kind of preparation method of aluminium manganese intermediate alloy |
| CN108103328A (en) * | 2017-12-15 | 2018-06-01 | 南通昂申金属材料有限公司 | A kind of preparation process of aluminium bismuth intermediate alloy |
| CN113481400A (en) * | 2021-05-26 | 2021-10-08 | 四川实美科技有限公司 | Deslagging flux with heating effect for smelting secondary aluminum and preparation method thereof |
| CN114703390B (en) * | 2022-06-06 | 2022-09-09 | 中国航发北京航空材料研究院 | Refining agent and refining and purifying method of aluminum alloy cast on line by combining refining agent with argon |
| CN115109961A (en) * | 2022-06-10 | 2022-09-27 | 徐州思源铝业有限公司 | Aluminum alloy rare earth refining agent and preparation method thereof |
| CN115029573A (en) * | 2022-06-10 | 2022-09-09 | 徐州思源铝业有限公司 | Aluminum alloy slag remover and preparation method thereof |
| CN115404374A (en) * | 2022-09-26 | 2022-11-29 | 湖北创伟科技股份有限公司 | Composite aluminum alloy refining agent and application method thereof |
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| CN103215465B (en) * | 2013-04-19 | 2014-09-24 | 扬州峰明金属制品有限公司 | Preparation method of rear-earth magnesium alloy product |
| CN103215468B (en) * | 2013-04-19 | 2015-01-14 | 扬州峰明金属制品有限公司 | Rear-earth magnesium alloy smelting agent and preparation method thereof |
| CN103266237B (en) * | 2013-06-07 | 2014-12-10 | 东南大学 | Deslagging smelting flux for smelting casting zinc alloy and preparation method thereof |
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