CN1197675C - Method for obtaining wide diameter liquid metal container-less contact fast coagulation - Google Patents
Method for obtaining wide diameter liquid metal container-less contact fast coagulation Download PDFInfo
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- CN1197675C CN1197675C CN 03101186 CN03101186A CN1197675C CN 1197675 C CN1197675 C CN 1197675C CN 03101186 CN03101186 CN 03101186 CN 03101186 A CN03101186 A CN 03101186A CN 1197675 C CN1197675 C CN 1197675C
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Abstract
The present invention discloses a method for obtaining wide diameter liquid metal containerless contact high undercooling rapid coagulation. In the method, medium cleaning smelting is carried out in silicon oil, by means of a rotary type on-off valve and the application of the pressure of 5 to 150Pa, liquid alloy is directly sprayed into an upright type condensing drop tube filled with silicon oil with the height larger than 0.8 meters, and liquid drops are rapidly coagulated during free falling without contact with the container wall. The method does not need any vacuum pumping system and various protective atmospheres, and the whole smelting and coagulation process is completed in a super clean environment, which has the advantages of enormously simplified system device, small device volume, very low manufacturing cost, low main device cost within 300 yuan, high heat exchange capability and high cooling speed, and can prepare high undercooling rapid coagulation metal particles with the diameter of 0.1mm to 6mm and wide size range in a drop tube with the height of 0.8 meters.
Description
Technical field:
The present invention relates to a kind of method of not having container contact high undercooling rapid solidification, exactly, it is applicable to Pb, Sn, Zn simple metal and Pb-Sb, Sn-Sb, Pb-Sn-Sb, Pb-Sn-Zn-Sb antifriction metal melting and the high undercooling rapid solidification in the clean environment of no container contact in clean environment.This method is except can carrying out the scientific research, but intuitive and convenient is used for liquid metal rapid solidification education experiment.
Technical background:
By retrieval as can be known: in the development process of solidification technology, high undercooling and rapid solidification are one of most active problems in the present material scientific and engineering research field, the industrial chilling flash set technology that widely adopts is owing to be subjected to the control of diabatic process can only prepare thickness or the minimum alloy of diameter, carry out the high speed atomizing as liquid towards metal in various natural instincts media and handle, prepare the minimum metal dust of size; With single roller get rid of the band method, two roller gets rid of the band method and prepares the chilling metal sheet band.In the laboratory, prepare micron-sized metallic with emulsion process.F.Giliessen; D.M.Herlach. " Crystal nucleation and glass-formingability of Cu-Zr in a containerless state " .Materials Scienceand Engineering.1988; 97:147-151. disclosedly bring out forming core in early days for what prevent that liquid metal oxidation in air from avoiding heterogeneous nucleus, high undercooling rapid solidification equipment all needs to be equipped with high vacuum system or carries out rapid solidification through behind the pumping high vacuum in protective atmospheres such as argon gas, helium, nitrogen.The employed equipment manufacturing cost costliness of said method, device are greatly and comparatively complicated.Xu Yingfan, Chen Hong, Wang Wenkui " 20m fall in the pipe mistake of Pd-Ni-P alloy cold with super saturated solid solution formation mutually ", Acta Physica Sinica, 1992,41 (7): the size of the disclosed chilling molten drop of 1111-1118. is little, size range is narrower.The equipment that is to say is big, and the particle size that obtains is little, and equipment needs pumping high vacuum in melting and process of setting, also must charge into protective gas, device volume cost height.
In recent ten years, development along with materials sciences in space, it should be noted that space environment is a microgravity, super clean, no container, can be liquid metal obtains high undercooling and solidifies ecotopia is provided, can obtain non-oxidation, even tissue, no proportion segregated solidification tissue, American-European, countries such as Russia have utilized the space space station to carry out the increment study of crystalline materials such as GaAs, yet in space, carry out metal to solidify research expenditure high, experiment is extremely limited, therefore, simulation space solidifies and paid attention to by various countries on the ground in recent ten years, the pipe of the falling tower method that falls is arranged, A.F.Norman, K.Eckler, A.Zambon et al.Application ofmicrostructure-selection maps to droplet solidification:acase study of the Ni-Cu system.Actamoter, 1998,46 (10): 3355-3370. discloses smelting in suspension method in the magnetic field, molten glass purification method, emulsion droplet method or the like, but its cooling velocity is low.In the experimental rig that simulation space solidifies, wherein simulating degree is higher is the pipe tower method that falls that falls, this method is with liquid metal (majority charges into argon gas after being to vacuumize) free-falling in the pipe that falls of high vacuum of fusion (many fall to pipe be that liquid metal is blown off), and drop is solidified in the landing process.The longest in the world tower that falls is that Japan utilizes useless 700 meters dark mines that fill to make at present, and the fall time that can be used for effectively experiment is 11 seconds.The liquid metal device melts in the container tank of sealing, then with the jar free-falling to the shaft bottom, China is at present at Chinese Academy of Sciences's mechanics institute newly-built 80 meters tower that falls in national microgravity research center, Inst. of Physics, CAS has 20 meters and falls to managing; Northwestern Polytechnical University materials sciences in space laboratory has 3 meters pipes that fall, and the molten drop fall time in 3 meters pipes that fall only has 0.7 second, and the liquid metal particle diameter that can obtain is less than 2mm.These appliance arrangement costs are high, study the height that need increase the pipe that falls that solidifies of larger-size liquid metal particle, and research and application are restricted.
Summary of the invention
The objective of the invention is antifriction metals such as Pb-Sb, Sn-Sb, Pb-Sn-Sb are purified melting in silicone oil, and in the vertical type that is full of silicone oil falls pipe, make it in the free settling process, realize no container contact high undercooling rapid solidification, the whole process of solidifying is finished in infall process, do not contact during this time with any chamber wall, promptly keep super clean environment, obtained quick cooled and solidified again.
The step of its realization of the present invention is as follows:
1. purify melting in silicone oil, opening-rotary opens and closes valve, by applying 5～150Pa pressure;
2. making liquid alloy is the nozzle of 0.5mm to 3mm by the aperture, and the condensation that the vertical type that directly sprays into 0.8 meter height is full of silicone oil falls in the pipe;
3. make drop not with the contact process of chamber wall in, in free settling, finish rapid solidification.
The present invention has following characteristics:
(1) whole melting and process of setting are all finished in super clean environment, the metallic no any oxidation in surface of solidifying, the surface-brightening cleaning, process of setting does not contact with solid-state chamber wall, thereby prevented that oxidation and the heterogeneous nucleus of chamber wall from bringing out the influence of forming core, makes liquid metal obtain high undercooling before solidifying.
(2) this method need not any pumped vacuum systems and various protective atmosphere, thereby has greatly simplified system and device, and equipment volume is little, and cost is extremely low, and agent set of the present invention is in 300 yuan.
(3) heat-exchange capacity height, cooling velocity are fast.The cooling velocity of liquid metal in silicone oil is higher than the cooling velocity that reaches in a vacuum in the various retentivity gases far away, thereby solidify in the container in the sedimentation of highly having only 0.8 meter, prepare large scale Pb-Sb, the Sn-Sb rapidly solidified alloy particle of diameter 6mm, the high undercooling rapid solidification is not only significant to scientific research to the large scale development, commercial Application is had even more important value, and this also is the at present domestic and international large-scale desired result who obtains of tower of falling.
The chilling metallic of the size range broadness that (4) can obtain.The present invention adopts the nozzle that oozes outspoken footpath 0.5mm to 3mm, can prepare the high undercooling rapidly solidified alloy of the various sizes of diameter 0.1mm～6mm.
(5) refinement alloy structure effect is remarkable, can eliminate the gravity segregation because of the difference in specific gravity generation of alloy constituent element.Its tissue has reached at present both at home and abroad the high vacuum refinement level of pipe to tissue that fall.
(6) clear glass melting chamber and transparent condenser are adopted in this experiment, can directly observe the overall process of fusing and sedimentation cooling, thereby can carry out the monitoring of temperature and sedimentation time easily and be used for teaching research intuitively.
The invention will be further described below with reference to accompanying drawing:
The present invention is used for the rapid solidification to Pb-Sb, Sn-Sb, Pb-Sn-Sb material for sliding bearing.
Fig. 1 is a no container contact high undercooling quick solidification apparatus schematic diagram of the present invention.
1 is particle collector in the drawings; 2 is room temperature silicone oil; 3 is upright glass coagulator; 4 is heater; 5 is high-temperature silicon oil; 6 is sealing-plug; 7 is the glass melting chamber; 8 is liquid metal; 9 is rotation gate; 10 is overfall; 11 is the silicone oil recipient; 12 is compression pump; 13 is firm banking; 14 is infrared radiation thermometer;
Fig. 2 is a Pb-15wt%Sb high undercooling rapid solidification particle pictorial diagram of the present invention.
Fig. 3 is a Sn-16wt%Sb high undercooling rapid solidification part large scale particle pictorial diagram of the present invention.
Fig. 4 is that Pb-11.2wt%Sb eutectic alloy different-diameter particle is from solidifying beginning to the calculated curve that finishes required time.
Fig. 5 is that Sn-10.4wt%Sb Peritectic Alloy different-diameter particle is from solidifying beginning to the calculated curve that finishes required time.
Fig. 6 is the relation curve of Pb-11.2wt%Sb eutectic alloy liquid-drop diameter and cooling velocity under the 550K temperature.
Fig. 7 is the relation curve of Sn-10.4wt%Sb Peritectic Alloy liquid-drop diameter and cooling velocity under the 550K temperature.
Fig. 8 is the Pb-11.2wt%Sb eutectic alloy thick tissue that (under the industrial condition) forms under slow curing condition, primary phase Sb is the bulk tip-angled shape, and more serious gravity segregation phenomenon has taken place, the Sb that proportion is little floats on the crucible top, and heavy Pb is sunken to the crucible below.
Fig. 9 when Pb-11.2wt%Sb eutectic alloy particle diameter D=4mm, organizes remarkable refinement under the fast curing condition of high undercooling of the present invention, the gravity segregation phenomenon is eliminated, and the growthform of facet phase Sb transforms to the rough interfaces growth.
When Figure 10 is Pb-11.2wt%Sb eutectic alloy particle diameter D=1.5mm, organize refinement significantly.
When Figure 11 was Pb-11.2wt%Sb eutectic alloy particle diameter D=0.7mm, 65% solidified structure formed with the explosion type rapid solidification, has formed superfine little eutectic structure, and outburst forming core district has typically " Sunny " growth characteristics.
Figure 12 is the quick nucleating center of a Pb-11.2wt%Sb eutectic alloy particle pattern.
Figure 13 is the thick tissue that the Sn-16wt%Sb alloy forms when slowly solidifying under industrial condition, Δ T=3 ℃.Primary phase SnSb compound is thick wedge angle bulk.
Gravity segregation also takes place in Figure 14 when Sn-16wt%Sb alloy graining speed is slow.ΔT＝12℃。
Figure 15 is under rapid solidification condition of the present invention, and when Sn-16wt%Sb alloy particle diameter D=3.7mm, primary phase SnSb is refinement significantly, and average diameter is for slowly solidifying 1/10 of size.The gravity segregation phenomenon is eliminated fully.
Figure 16 is when Sn-16wt%Sb alloy particle diameter D=0.1mm, and primary phase SnSb compound average diameter is refined to 1um.
Below be specific embodiments of the invention
Adopt energy conservation law, Lumped-Capacity method and newton's cooling jig that the cooling capacity of contrive equipment is calculated.
(1) drop of different-diameter is from solidifying beginning to solidifying the end required time
Fig. 4 is that the Pb-11.2wt%Sb eutectic alloy is when liquid-drop diameter increases to 5mm by 0.1mm, drop is in room temperature silicone oil, finish the required time from solidifying beginning to solidifying, as can be seen, when liquid-drop diameter is 1mm, needed setting time is 0.3 second only, and setting time is 1.08 seconds when liquid-drop diameter increases to 5mm, and Fig. 5 is a Sn-10.4wt%Sb Peritectic Alloy different-diameter droplet solidification required time.Because the fusing point of above-mentioned two alloys differs little, so the setting time of calculating is more or less the same.
(2) cooling velocity of drop in silicone oil
Fig. 6, Fig. 7 be respectively Pb-11.2wt%Sb eutectic alloy and Sn-10.4wt%Sb Peritectic Alloy when the 550K temperature, the cooling velocity of different-diameter drop in silicone oil.Can see that when liquid-drop diameter D=0.1mm, cooling velocity V has all reached 1 * 10
5More than the k/s, when liquid-drop diameter D=4mm, cooling velocity V has reached 3.1 * 10
2More than the K/S.
The size of the high undercooling of 1.Pb-15wt%Sb material for sliding bearing and rapid solidification particle and pattern.
Fig. 2 is the Pb-15wt%Sb alloy particle of high undercooling rapid solidification.Can prepare the rapid solidification particle of diameter 0.1mm to 6mm diameter by changing the drip nozzle diameter, the no any oxide of alloy particle surface cleaning light.
Tissue topography:
Fig. 8 to Figure 12 is one group of tissue topography that the Pb-15wt%Sb alloy forms under different curing conditions.
When the Pb-15wt%Sb antifriction metal solidifies under the general industry condition, serious gravity segregation takes place, heavy Pb sinks to the bottom of crucible, and the less Sb of proportion floats on top, cause macroscopical uneven distribution of material structure, simultaneously, primary phase Sb presents the block distribution of thick wedge angle, alloy through no container contact high undercooling rapid solidification, each no proportion segregation that is evenly distributed mutually in its tissue, the remarkable refinement of primary phase Sb, its pattern with the solidified particles diameter to reduce be the increase of degree of supercooling, be dendritic growth by massive transformation gradually, the growth of symbiosis completely is up to being refined into spherical Sb particle.See the tissue topography among Fig. 9 to Figure 12.Wherein Figure 12 is the rapid solidification particle of diameter 1mm, and the crystallization of primary phase Sb is suppressed, and has generated the eutectic structure pattern of ultra-fineization.This tissue is down unfrequented in serious offense, and the result of outburst forming core has reached domestic and international high vacuum and fallen to managing same rapid solidification effect.
The high undercooling of 2.Sn-16wt%Sb material for sliding bearing and rapid solidification
(1) size of rapid solidification particle and pattern
The Sn-16wt%Sb alloy was a Peritectic Alloy.Experimental result and Pb-15wt%Sb be hypereutectic to be closed identically, has obtained diameter 0.1mm to 5mm high undercooling rapid solidification particle in the device of this experiment equally.Fig. 3 be wherein size than the pattern of macroparticle, the surface no any oxidation.
(2) rapid solidification tissue topography
Figure 13 is the tissue of Sn-16wt%Sb alloy under slow curing condition, and primary phase SnSb compound forms thick wedge angle massive phase, and size is about 100 μ m, and Figure 15,16 is respectively that diameter is to obtain tissue under 3.7mm and the 0.1mm high undercooling rapid solidification condition.Can see, along with the solidified particles diameter to reduce be the increase of degree of supercooling, the refinement gradually of the size of SnSb primary phase, even tiny being distributed in the matrix, and its pattern is changed into tiny granular by the wedge angle massive phase, and the size of primary phase SnSb is refined to 30 μ m among Figure 15, the size average out to 3 μ m of primary phase SnSb among Figure 16, be 1/30 of size under the slow curing condition, present in the matrix that the disperse shape is distributed in alloy.Thinning effect is very remarkable.This spherical particle will reduce the effect of isolating to matrix.
The liquid metal that purifies melting by rotary switching valve, is directly injected condensation that vertical type the is full of silicone oil pipe that falls.The condensation that vertical type is full of silicone oil falls the pipe height greater than 0.8 meter.The wide size range rapidly solidified alloy of preparation diameter 0.1～6mm in the pipe that falls of 0.8m.Melting and solidify overall process and all do not adopt to vacuumize and handle and inert gas shielding.Working chamber, switching valve and condenser pipe all adopt transparent glass material to make.
Claims (3)
1. one kind obtains the method that the wide diameter liquid metal does not have container contact rapid solidification, and the step of its realization is as follows:
1. purify melting in silicone oil, opening-rotary opens and closes valve, by applying 5～150Pa pressure;
2. making liquid alloy is the nozzle of 0.5mm to 3mm by the aperture, and the condensation that the vertical type that directly sprays into 0.8 meter height is full of silicone oil falls in the pipe;
3. make drop not with the contact process of chamber wall in, in free settling, finish rapid solidification.
2. a kind of method that the wide diameter liquid metal does not have container contact rapid solidification that obtains according to claim 1 is characterized in that: melting and solidify overall process and all do not adopt to vacuumize and handle and inert gas shielding.
3. a kind of method that the wide diameter liquid metal does not have container contact rapid solidification that obtains according to claim 1, it is characterized in that: working chamber, switching valve and condenser pipe all adopt transparent glass material to make.
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| CN 03101186 CN1197675C (en) | 2003-01-17 | 2003-01-17 | Method for obtaining wide diameter liquid metal container-less contact fast coagulation |
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| CN106735265A (en) * | 2016-11-17 | 2017-05-31 | 安顺市虹翼特种钢球制造有限公司 | Method for processing steel ball |
| CN107589145B (en) * | 2017-09-04 | 2020-08-25 | 西北工业大学 | Microgravity solidification device for metal droplets |
| CN107803509B (en) * | 2017-09-28 | 2019-12-31 | 兰州理工大学 | Ball manufacturing device by vacuum weightlessness method and operation method thereof |
| CN108168994B (en) * | 2017-11-27 | 2020-03-20 | 西北工业大学 | Device for solidifying metal liquid drops under free falling condition |
| CN111230130B (en) * | 2020-03-02 | 2021-09-07 | 西北工业大学 | Rapid solidification system and method for suspending large-size metal droplets under microgravity condition |
| CN111346572B (en) * | 2020-03-18 | 2022-06-21 | 上海理工大学 | Method for controlling shape of solidified liquid drop and application |
| CN113500214B (en) * | 2021-07-06 | 2022-07-01 | 西北工业大学 | Real-time capturing system for simulating metal droplet chasing fusion process under microgravity |
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