CN103924130B - A kind of aluminium alloy/316L stainless steel coating matrix material and preparation method thereof - Google Patents
A kind of aluminium alloy/316L stainless steel coating matrix material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of aluminium alloy/316L stainless steel coating matrix material and preparation method thereof, this matrix material comprises alloy matrix aluminum and is sprayed on the 316L stainless steel coating that aluminium alloy matrix surface thickness is 40 ~ 60 μm; Alloy matrix aluminum material composition comprises: the iron of 6 ~ 10wt%, the mishmetal of 2 ~ 6wt%, and surplus is aluminium and inevitable impurity; First melting Al-Fe master alloy and Al-Re master alloy; To pour into a mould the aluminium alloy cast ingot that cooling and demolding obtains comprising 6 ~ 10wt% iron and 2 ~ 6wt% mishmetal after fine aluminium ingot, Al-Fe master alloy and the melting of Al-Re master alloy; After alloy cast ingot crushing washing, reaction-injection moulding prepares aluminum alloy round ingot, and hot-pressing densification, obtain alloy matrix aluminum, adopt hypersonic flame spraying technology on alloy matrix aluminum, prepare 316L stainless steel coating.Compared with prior art, alloy matrix aluminum/316L stainless steel coating matrix material that prepared by the present invention have coating uniform, coating and basal body binding force strong, conduct electricity very well, the advantage such as internal resistance is little, good corrosion resistance, coating compactness are good.
Description
Technical field
The present invention relates to a kind of aluminium alloy and stainless steel composite material and preparation method thereof, especially relate to a kind of aluminium alloy/316L stainless steel coating matrix material and preparation method thereof.
Background technology
Sodium-sulfur cell is a kind of secondary cell of excellent performance, has many original advantages, is mainly reflected in: 1. specific energy is high, and its theoretical specific energy is 760WhKg
-1, reality is greater than 300WhKg
-1, be 3 ~ 4 times of lead-acid cell; 2. power density is high, cell maximum capacity for energy storage reaches 650 ampere-hours, more than power 120W, little module can be formed by after multiple battery cell combination, its power is generally tens of kilowatt, can energy storage be directly used in, little module be carried out superposing the energy storage station that just can form different capacity size again according to the specific requirement that electric power exports; 3. efficiency for charge-discharge is high, and owing to adopting solid electrolyte, do not have self-discharge phenomenon, charging efficiency almost can reach 100%, and the duration of charging is short; 4. environmental friendliness, battery is friction noiseless at work, does not have gas reaction to produce, and expection has longer service life cycle, and adopts all-sealed structure, does not have disposal of pollutants; 5. structure is simple, easily manufactures, easy to maintenance and cost is low; 6. the abundance of material, low price etc., because sodium-sulfur cell has numerous advantages, become at present one of the most promising static energy-storage battery, application in recent years in the power system comprising Japan, the U.S., Europe is rapidly developed, and has huge application prospect in the having of electrical power trans mission/distribution system, reactive power support and Multifunctional electric energy storage system.
Sodium-sulfur cell development in recent years is very fast, but is also faced with a lot of bottlenecks and technological difficulties, and wherein the selection of sulfur electrode container is exactly very crucial one.The corrosion of sodium-sulfur cell sulphur pole container causes one of battery performance decline, the important factor affecting battery life.Sulphur and the reaction product sodium polysulphide of the extremely middle melting of battery sulphur have severe corrosive, and it and metal vessel can react and form loosely organized metallic sulfide, affect physics and the chemical property of battery, cause cell performance degradation.Sodium-sulfur cell adopts center sodium structure to obtain higher specific energy density usually, and like this, battery case materials serves as again the collector of sulphur pole simultaneously, and this just requires that sulphur pole collector/case material possesses excellent corrosion resistance and long-term chemical stability; Sufficiently high electronic conductivity; Good to sodium polysulphide wettability, and nonwetting to sulphur; Enough physical strengths and good workability; Quality is little as far as possible, and cost is low as far as possible;
The sulphur pole container of current domestic use is Stainless Steel Shell substantially, and the 316L stainless steel that the first-generation sodium-sulfur cell product comprising the sodium-sulfur battery energy storage system put on display during Shanghai World's Fair for 2010 and the Shanghai Electric Sodium-Sulfur Energy Storage Technology Co., Ltd. set up for 2011 all adopts is as sulphur pole collector.Stainless hot strength is good, and electroconductibility and erosion resistance all temporarily can meet the demands.But stainless steel also faces some problems as sulphur pole collector: (1) stainless price costly causes cost higher; (2) quality is unfavorable for that greatly sodium-sulfur cell is assembled on a large scale, carries; (3) Hattori (S.Hattofi, M.Yamaura, S.Kimura, etal.ProceedingsSAECongress, Detroit, 1997, paper770281) etc. find in center sodium structure battery, to adopt the battery phase specific storage of Stainless Steel Shell to have dropped 50% after 100 circulations, can there is local corrosion in some position of housing, if perforation, abnormally dangerous; (4) as the collector of battery, thick and heavy electric resistance of stainless rate is at high temperature also still higher, and thermal conductivity and electroconductibility all have much room for improvement.
If the erosion resistance that 316L stainless steel is good can be utilized, play the advantage of aluminium alloy simultaneously, promote its corrosion resistance nature, problem faced by above-mentioned just can solve, and 316L stainless steel is prepared into uniform coating through thermospray, saves lot of materials, quality alleviates greatly, and thermal conduction becomes rapider, and the overall electrical resistance of battery also reduces much, is also the effective ways promoting corrosion resistance of aluminum alloy.
In addition, because transiting group metal elements and the bright-coloured series elements alloying element solid solubility when liquid state is high, time solid-state, solid solubility is very low and have lower spread coefficient, therefore the limit solid solubility of these elements in aluminium can effectively be improved by flash set technology, the diffusing particle of sufficient amount can be formed in the alloy, form heat-resisting aluminium alloy.With adopt traditional casting or cast compared with material prepared by deformation processing technique, it organizes obvious refinement, more tiny and the more disperse that distributes of precipitated phase, and segregation obtains effective control, thus improve every mechanical property of alloy significantly, compared with traditional Rapid Solidification Powder metallurgical technology, can directly form finished product or work in-process, eliminate powder preparation, store transport, the multiple tracks production processes such as sintering, therefore the oxidation of material can effectively be reduced, and the preparation cost of material is significantly reduced, therefore sprayup process is the very potential method of one of preparation high-performance Al-Fe system alloy.
Summary of the invention
Object of the present invention be exactly provide to overcome defect that above-mentioned prior art exists ~ kind of coating uniform, coating and basal body binding force by force, conduct electricity very well, internal resistance is little, the aluminium alloy of corrosion resistance and good/316L stainless steel coating matrix material and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions:
A kind of aluminium alloy/316L stainless steel coating matrix material, this matrix material comprises alloy matrix aluminum and is sprayed on the 316L stainless steel coating of aluminium alloy matrix surface; Wherein the thickness of 316L stainless steel coating is 40 ~ 60 μm;
Described alloy matrix aluminum material composition comprises: the iron of 6 ~ 10wt%, the mishmetal of 2 ~ 6wt%, and surplus is aluminium and inevitable impurity, is expressed as Al-(6 ~ 10) Fe-(2 ~ 6) Re by elementary composition; Wherein Re represents mishmetal.
As preferably, described alloy matrix aluminum material comprises: the iron of 8wt%, the mishmetal of 4wt%, and surplus is aluminium and inevitable impurity, is expressed as Al-8Fe-4Re by elementary composition.
Described mishmetal is lanthanum-cerium mishmetal, and composition comprises: La32 ~ 33wt%, Ce62 ~ 63wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity.
As preferably, described mishmetal composition comprises: La32.6wt%, Ce62.6wt%, O1.6wt%, F0.3wt%, Fe0.54wt%, Al0.39wt%, Mg0.24wt%, P0.17wt%, Cl0.16wt%, Zn0.12wt% and inevitably impurity.
A preparation method for aluminium alloy/316L stainless steel coating matrix material, comprises the following steps:
(1) fusing point due to iron is higher, rare earth metal is also easily oxidized in extractive process, institute thinks minimizing melting loss of elements and oxidation, first with fine aluminium ingot and pure iron rod for raw material uses medium-frequency induction furnace melting Al-Fe master alloy, wherein in Al-Fe master alloy, the content of Fe is 20wt%, is expressed as Al-20Fe by elementary composition; With fine aluminium ingot and mishmetal for raw material uses well formula crucible electrical resistance furnace melting Al-Re master alloy, Re represents mishmetal, and in Al-Re master alloy, the content of Re is 10wt%, is expressed as Al-10Re by elementary composition;
Described fine aluminium ingot is the technical grade aluminium ingot that purity is not less than 99.95wt%, described pure iron rod for diameter that iron level is not less than 99.99wt% be the technical pure iron staff of 5mm, described mishmetal is lanthanum-cerium mishmetal, composition comprises: La32 ~ 33wt%, Ce62 ~ 63wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity;
(2) by the iron of 6 ~ 10wt%, the mishmetal of 2 ~ 6wt%, surplus is the composition proportion of aluminium and inevitable impurity, get fine aluminium ingot, Al-Fe master alloy in medium-frequency induction furnace, Al-Re master alloy is added again after fusing, mix, pour into a mould cooling and demolding afterwards and obtain the aluminium alloy cast ingot comprising 6 ~ 10wt% iron and 2 ~ 6wt% mishmetal;
(3) aluminium alloy cast ingot cleaning: aluminium alloy cast ingot melting obtained is broken, the block alloy of fragmentation is put into successively acetone soln and spirituous solution ultrasonic cleaning, dries stand-by after taking-up;
(4) reaction-injection moulding prepares aluminum alloy round ingot: by cleaning block alloy Frequency Induction Heating to 1100 ~ 1300 DEG C obtained in step (3), make it melt, then with N
2for atomizing gas, under atomization pressure is 0.8-1.5Mpa, reaction-injection moulding prepares aluminum alloy round ingot, and detailed process is as follows:
The crucible that the block alloy obtained puts into spray deposition equipment will be cleaned in step (3); wherein crucible uses magnesia crucible; crucible bottom is silicon nitride thrust-augmenting nozzle; to block alloy carry out Frequency Induction Heating to 1100 ~ 1300 DEG C; block alloy is melted; melt after thawing, under protection of inert gas, carries out atomization by the thrust-augmenting nozzle coordinated with Double layer non-limited airflow atomizing nozzle separate type and is shaped, and atomizing gas is N
2, atomization pressure is 0.8 ~ 1.5Mpa, and melt mass flow rate in thrust-augmenting nozzle is 1.7 ~ 1.8kg/min, atomization distance is 400 ~ 500mm, and while atomization, bottom deposit dish rotates with the rotating speed of per minute 45 ~ 120 turns, melt deposition, on bottom deposit dish, obtains aluminum alloy round ingot;
(5) hot-pressing densification: hot-pressing densification is carried out to the aluminum alloy round ingot that step (4) obtains, the pressuring method of hot-pressing densification is unidirectional pressurization, hot pressing pressure is set to 300 ~ 500Mpa, hot pressing temperature is 250 ~ 450 DEG C, soaking time 1 ~ 3h, obtain the jet deposition aluminium alloy of densification, i.e. alloy matrix aluminum;
(6) 316L stainless steel coating is prepared: before spraying, the alloy matrix aluminum obtained step (5) cleans to remove greasy dirt and other dirts of specimen surface, then sandblast machine is utilized to use emergy to carry out sandblasting to aluminium alloy matrix surface, increase surfaceness, improve the bonding strength between 316L stainless steel coating and alloy matrix aluminum.Subsequently, adopt hypersonic flame spraying technology on alloy matrix aluminum, prepare 316L stainless steel coating, obtain aluminium alloy/316L stainless steel coating matrix material.The metal-powder of preparation 316L stainless steel coating uses granularity to be 325-500 object 316L powder of stainless steel, spray with propane-oxygen mix burning as thermal source, main technologic parameters is as follows: propane pressure is 0.6 ~ 0.7Mpa, flow is 65 ~ 100L/min, oxygen pressure is 0.8 ~ 1.5Mpa, and flow is 150 ~ 170L/min; Powder particle speed 550 ~ 650m/s in flame gun.
The aluminium alloy prepared/316L stainless steel coating matrix material is carried out Performance Detection, being comprised: the tissue topography of (1) coating characterizes; (2) micro-hardness testing; (3) bonding strength test; (4) resistivity of coating: (5) static corrosion is tested.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention adopts metallic aluminium as the main raw material of matrix material, and it is cheap, easy machine-shaping, light weight not only, and specific conductivity is also very high.
(2) because lanthanum-cerium mishmetal has little solubleness and low velocity of diffusion in aluminum substrate, and binary and the Ternary intermetallic compounds of high-volume fractional can be formed, play dispersion-strengthened action, alloy is made to have higher intensity and thermostability, therefore the present invention is when designing alloying constituent, add bright-coloured-cerium mishmetal, utilize Guo Du race metallic element and the bright-coloured series elements solid solubility when liquid state high, time solid-state, solid solubility is very low and have the characteristic of lower diffusion system, the limit solid solubility of bright-coloured-cerium mixed rare-earth elements in aluminium effectively can be improved by flash set technology, the diffusing particle of sufficient amount can be formed in the alloy, prepare alloy matrix aluminum.
(3) the present invention adopts spray up n. technology to prepare the aluminum alloy materials comprising 6 ~ 10wt% iron and 2 ~ 6wt% mishmetal, the atomization process of metal is combined with moulding process, realize the once shaped of large size rapidly solidified material Jin Shuhuohejinrongtiyi104～106 DEG C/s, directly produce from liquid metal and there is rapid solidification structure, overall fine and close high performance material.
(4) first the present invention prepares Al-Fe master alloy and Al-Re master alloy, and then with Al-Fe master alloy and Al-Re master alloy for the aluminium alloy that the iron, the mishmetal of 2 ~ 6wt%, the surplus that comprise 6 ~ 10wt% is aluminium prepared by raw material, the advantage of this technique is better to add Fe and Re in Al, to prevent scaling loss and the oxidation of Fe and Re.
(5) the present invention adopts spray deposition processing to prepare to comprise the iron of 6 ~ 10wt%, the mishmetal of 2 ~ 6wt%, surplus to be the aluminium alloy of aluminium, avoids Powder Oxidation, technique simple and cost is low.
(6) the present invention adopts hypersonic flame spraying technology to prepare 316L stainless steel coating, alloy matrix aluminum/316L stainless steel coating the matrix material obtained has the following advantages: 1. coating uniform, conduct electricity very well compared with 316L stainless steel, internal resistance is little many; 2. coating and basal body binding force strong; 3. thermal spray process is convenient, and technique is simple; 4. there is good erosion resistance; 5. coating is fine and close.
Accompanying drawing explanation
Fig. 1 is the structural representation that in the present invention, reaction-injection moulding uses equipment;
Fig. 2 is the front 316L stainless steel coating surface topography Electronic Speculum figure of corrosion in embodiment 1;
Fig. 3 is the front 316L stainless steel coating Cross Section Morphology Electronic Speculum figure of corrosion in embodiment 1;
Fig. 4 is the rear 316L stainless steel coating surface topography low power Electronic Speculum figure of corrosion in embodiment 1;
Fig. 5 is the rear 316L stainless steel coating surface topography high power Electronic Speculum figure of corrosion in embodiment 1;
Fig. 6 is the XRD figure in embodiment 1 before the corrosion of 316L stainless steel coating;
Fig. 7 is the XRD figure in embodiment 1 after the corrosion of 316L stainless steel coating.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Purity is not less than the fine aluminium ingot of 99.5wt%, pure iron rod and block lanthanum-cerium mishmetal (composition is in table 1) and is mixed with appropriate mass percent the Al-Re master alloy that the Al-Fe master alloy that is divided into Al-20Fe and composition are Al-10Re, each meter 5 kilograms; Use medium-frequency induction furnace melting Al-Fe master alloy, use well formula crucible electrical resistance furnace melting Al-Re master alloy.Then according to the composition proportion of Al-8Fe-4Re, get appropriate fine aluminium ingot, Al-Fe master alloy is placed in medium-frequency induction furnace, add Al-Re master alloy again after fusing, and induction stirring mixes, pour into a mould cooling and demolding afterwards and obtain casting Al-8Fe-4Re alloy cast ingot.Alloy cast ingot fragmentation melting obtained, puts into acetone soln successively by the block alloy of fragmentation and spirituous solution carries out ultrasonic cleaning, naturally dries after taking out; The block alloy that cleaning obtains is put into the crucible of the large-scale spray deposition equipment (as shown in Figure 1) of developing voluntarily, Frequency Induction Heating to melt temperature is 1100 ~ 1200 DEG C, N
2atomization pressure is 1.3Mpa, preparation Al-8Fe-4Re alloy.Use magnesia crucible, crucible bottom is silicon nitride water conservancy diversion, and draft-tube diameter is 3mm, adopt Double layer non-limited airflow atomizing nozzle, melt mass flow rate is about 1.78kg/min through measuring and calculating, and atomization distance is 400mm, and bottom deposit dish rotating speed is per minute 45 turns.SYE-2000 type pressure testing machine and homemade heating temperature control device and mould is adopted to carry out hot-pressing densification to deposition ingot, pressuring method is unidirectional pressurization, and hot pressing pressure is set to 500Mpa, and hot pressing temperature is 250 DEG C, soaking time 2h, obtains the jet deposition Al-8Fe-4Re alloy of densification.After the Al-8Fe-4Re alloy base material of acquisition being carried out cleaning oil removing, the process of surface sand-blasting increase roughness, adopt hypersonic flame spraying technology to prepare 316L stainless steel coating on Al-8Fe-4Re alloy substrate, the thickness of 316L stainless steel coating is 56.7 μm.Spray with propane-oxygen mix burning for thermal source, main technologic parameters is as follows: propane pressure is 0.65Mpa, and flow is 80L/min, and oxygen pressure is 0.9Mpa, and flow is 155L/min; Powder particle speed 600m/s in flame gun.
In the present embodiment, reaction-injection moulding uses the structure of equipment as shown in Figure 1, induction heating crucible 4 and tundish 5 is provided with from top to bottom successively outside the top of cavity 1, induction heating crucible 4 is provided with protective atmosphere cover 3 with the outside of tundish 5, the outlet of tundish 5 connects thrust-augmenting nozzle 6, the exit of thrust-augmenting nozzle 6 is provided with Double layer non-limited airflow atomizing nozzle 7, the exit end of thrust-augmenting nozzle 6 is positioned at the centre of Double layer non-limited airflow atomizing nozzle 7, Double layer non-limited airflow atomizing nozzle 7 is connected with spraying gun pipeline 2, it is separate type fit system between thrust-augmenting nozzle 6 and Double layer non-limited airflow atomizing nozzle 7, it is inner that bottom deposit dish 10 is located at cavity 1, molten metal is in induction heating crucible 4 after induction heating, pour into tundish 5, be atomized by Double layer non-limited airflow atomizing nozzle 7 through thrust-augmenting nozzle 6, atomization metal 8 enters into after in cavity 1, be deposited on bottom deposit dish 10, form deposit preform billet 9.
Table 1 lanthanum-cerium mishmetal becomes to be grouped into
Aluminium alloy/316L stainless steel coating the matrix material obtained to the present embodiment carries out Performance Detection, and as shown in Figure 2, Cross Section Morphology as shown in Figure 3 for 316L stainless steel coating surface topography.Surface topography after the 316L stainless steel coating that the present embodiment obtains is corroded after using as shown in Figure 4, Figure 5.Found out by Fig. 2 ~ Fig. 5,316L stainless steel coating is little at the front and rear surfaces topographical difference that is corroded, and illustrates that 316L stainless steel coating has good erosion resistance.As shown in Figure 6, the XRD figure after the 316L stainless steel coating that the present embodiment obtains is corroded after using as shown in Figure 7 for the XRD figure of the 316L stainless steel coating that the present embodiment obtains.
The material property of the aluminium alloy that the present embodiment obtains/316L stainless steel coating matrix material is as shown in table 2 Yu table 3.
The hardness value (HV0.3) of table 2 aluminium alloy/316L stainless steel coating matrix material and bonding strength
The square resistance of table 3 aluminium alloy/316L stainless steel coating matrix material
Embodiment 2
Purity is not less than the fine aluminium ingot of 99.5wt%, pure iron rod and block lanthanum-cerium mishmetal (composition is in table 1) to be mixed with appropriate mass percent and to be divided into Al-20Fe, Al-10Re master alloy, each meter 5 kilograms; Use medium-frequency induction furnace melting Al-20Fe master alloy, use well formula crucible electrical resistance furnace melting Al-10Re master alloy.Then according to the composition proportion of Al-8Fe-4Re, get appropriate fine aluminium ingot, Al-Fe master alloy is placed in medium-frequency induction furnace, add Al-Re master alloy again after fusing, and induction stirring mixes, pour into a mould cooling and demolding afterwards and obtain casting Al-8Fe-4Re alloy cast ingot.Alloy cast ingot fragmentation melting obtained, puts into acetone soln successively by the block alloy of fragmentation and spirituous solution carries out ultrasonic cleaning, naturally dries after taking out; The block alloy that cleaning obtains is put into the crucible of the large-scale spray deposition equipment developed voluntarily, Frequency Induction Heating to melt temperature is 1100 DEG C ~ 1200 DEG C, N
2atomization pressure is 1.3Mpa, preparation Al-8Fe-4Re alloy.Use magnesia crucible, crucible bottom is silicon nitride water conservancy diversion, and draft-tube diameter is 3mm, adopt Double layer non-limited airflow atomizing nozzle, melt mass flow rate is about 1.78kg/min through measuring and calculating, and atomization distance is 450mm, and bottom deposit dish rotating speed is per minute 90 turns.SYE-2000 type pressure testing machine and homemade heating temperature control device and mould is adopted to carry out hot-pressing densification to deposition ingot, pressuring method is unidirectional pressurization, hot pressing pressure is set to 500Mpa, hot pressing temperature is 300 DEG C, soaking time 1.5min, obtains the jet deposition Al-8Fe-4Re alloy of densification.After the Al-8Fe-4Re alloy base material of acquisition being carried out cleaning oil removing, the process of surface sand-blasting increase roughness, adopt hypersonic flame spraying technology to prepare 316L stainless steel coating on Al-8Fe-4Re alloy substrate, the thickness of 316L stainless steel coating is 52.6 μm.Spray with propane-oxygen mix burning for thermal source, main technologic parameters is as follows: propane pressure is 0.6Mpa, and flow is 65L/min, and oxygen pressure is 1.0Mpa, and flow is 150L/min; Powder particle speed 650m/s in flame gun.
The material property of the aluminium alloy that the present embodiment obtains/316L stainless steel coating matrix material is as shown in table 4 Yu table 5.
The hardness value (HV0.3) of table 4 aluminium alloy/316L stainless steel coating matrix material and bonding strength
The square resistance of table 5 aluminium alloy/316L stainless steel coating matrix material
Alloy matrix aluminum/316L stainless steel coating matrix material prepared by the present embodiment has the following advantages: 1. coating uniform, conducts electricity very well compared with 316L stainless steel, and internal resistance is little many; 2. coating and basal body binding force strong; 3. thermal spray process is convenient, and technique is simple; 4. there is good erosion resistance; 5. coating is fine and close.
Embodiment 3
Purity is not less than the fine aluminium ingot of 99.5wt%, pure iron rod and block lanthanum-cerium mishmetal to be mixed with appropriate mass percent and to be divided into Al-20Fe, Al-10Re master alloy, each meter 5 kilograms; Use medium-frequency induction furnace melting Al-20Fe master alloy, use well formula crucible electrical resistance furnace melting Al-10Re master alloy.Then according to the composition proportion of Al-8Fe-4Re, get appropriate Al-Fe master alloy and be placed in medium-frequency induction furnace, add Al-Re master alloy again after fusing, and induction stirring mixes, pour into a mould cooling and demolding afterwards and obtain casting Al-8Fe-4Re alloy cast ingot.Alloy cast ingot fragmentation melting obtained, puts into acetone soln successively by the block alloy of fragmentation and spirituous solution carries out ultrasonic cleaning, naturally dries after taking out; The block alloy that cleaning obtains is put into the crucible of the large-scale spray deposition equipment developed voluntarily, Frequency Induction Heating to melt temperature is 1200 ~ 1300 DEG C, N
2atomization pressure is 1.1Mpa, preparation Al-8Fe-4Re alloy.Use magnesia crucible, crucible bottom is silicon nitride water conservancy diversion, and draft-tube diameter is 3mm, adopt Double layer non-limited airflow atomizing nozzle, melt mass flow rate is about 1.78kg/min through measuring and calculating, and atomization distance is 500mm, and bottom deposit dish rotating speed is per minute 120 turns.SYE-2000 type pressure testing machine and homemade heating temperature control device and mould is adopted to carry out hot-pressing densification to deposition ingot, pressuring method is unidirectional pressurization, and hot pressing pressure is set to 500Mpa, and hot pressing temperature is 350 DEG C, soaking time 1h, obtains the jet deposition Al-8Fe-4Re alloy of densification.After the Al-8Fe-4Re alloy base material of acquisition being carried out cleaning oil removing, the process of surface sand-blasting increase roughness, adopt hypersonic flame spraying technology to prepare 316L stainless steel coating on Al-8Fe-4Re alloy substrate, the thickness of 316L stainless steel coating is 56.3 μm.Spray with propane-oxygen mix burning for thermal source, main technologic parameters is as follows: propane pressure is 0.7Mpa, and flow is 100L/min, and oxygen pressure is 1.5Mpa, and flow is 170L/min; Powder particle speed 800m/s in flame gun.
The material property of the aluminium alloy that the present embodiment obtains/316L stainless steel coating matrix material is as shown in table 6 Yu table 7.
The hardness value (HV0.3) of table 6 aluminium alloy/316L stainless steel coating matrix material and bonding strength
The square resistance of table 7 aluminium alloy/316L stainless steel coating matrix material
Alloy matrix aluminum/316L stainless steel coating matrix material prepared by the present embodiment has the following advantages: 1. coating uniform, conducts electricity very well compared with 316L stainless steel, and internal resistance is little many; 2. coating and basal body binding force strong; 3. thermal spray process is convenient, and technique is simple; 4. there is good erosion resistance; 5. coating is fine and close.
Embodiment 4
A kind of aluminium alloy/316L stainless steel coating matrix material, this matrix material comprises alloy matrix aluminum and is sprayed on the 316L stainless steel coating of aluminium alloy matrix surface; The thickness of 316L stainless steel coating is 40.3 μm, and alloy matrix aluminum material composition comprises: the iron of 6wt%, the mishmetal of 2wt%, and surplus is aluminium and inevitable impurity, is expressed as Al-6Fe-2Re by elementary composition; Wherein Re represents mishmetal.Mishmetal is lanthanum-cerium mishmetal, and composition comprises: La32wt%, Ce62wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity.
The preparation method of above-mentioned aluminium alloy/316L stainless steel coating matrix material, comprises the following steps:
(1) with fine aluminium ingot and pure iron rod for raw material uses medium-frequency induction furnace melting Al-Fe master alloy, wherein in Al-Fe master alloy, the content of Fe is 20wt%; With fine aluminium ingot and mishmetal for raw material uses well formula crucible electrical resistance furnace melting Al-Re master alloy, Re represents mishmetal, and in Al-Re master alloy, the content of Re is 10wt%;
Fine aluminium ingot is the technical grade aluminium ingot that purity is not less than 99.95wt%, pure iron rod for diameter that iron level is not less than 99.99wt% be the technical pure iron staff of 5mm;
(2) by the iron of 6wt%, the mishmetal of 2wt%, surplus is the composition proportion of aluminium and inevitable impurity, get fine aluminium ingot, Al-Fe master alloy in medium-frequency induction furnace, Al-Re master alloy is added again after fusing, mix, pour into a mould cooling and demolding afterwards and obtain the aluminium alloy cast ingot comprising 6wt% iron and 2wt% mishmetal;
(3) aluminium alloy cast ingot cleaning: aluminium alloy cast ingot melting obtained is broken, the block alloy of fragmentation is put into successively acetone soln and spirituous solution ultrasonic cleaning, dries stand-by after taking-up;
(4) reaction-injection moulding prepares aluminum alloy round ingot: by cleaning the block alloy Frequency Induction Heating to 1100 DEG C obtained in step (3), make it melt, then with N
2for atomizing gas, under atomization pressure is 0.8Mpa, reaction-injection moulding prepares aluminum alloy round ingot, and detailed process is as follows:
The crucible that the block alloy obtained puts into spray deposition equipment will be cleaned in step (3); wherein crucible uses magnesia crucible; crucible bottom is silicon nitride thrust-augmenting nozzle; draft-tube diameter is 3mm; carry out Frequency Induction Heating to 1100 DEG C ~ 1200 DEG C to block alloy, block alloy is melted, and the melt after thawing is under protection of inert gas; carry out atomization by the thrust-augmenting nozzle coordinated with Double layer non-limited airflow atomizing nozzle separate type to be shaped, atomizing gas is N
2, atomization pressure is 0.8Mpa, and melt mass flow rate in thrust-augmenting nozzle is 1.7kg/min, and atomization distance is 400mm, and while atomization, bottom deposit dish rotates with the rotating speed of per minute 45 turns, and melt deposition, on bottom deposit dish, obtains aluminum alloy round ingot;
(5) hot-pressing densification: hot-pressing densification is carried out to the aluminum alloy round ingot that step (4) obtains, the pressuring method of hot-pressing densification is unidirectional pressurization, hot pressing pressure is set to 300Mpa, hot pressing temperature is 250 DEG C, soaking time 1h, obtain the jet deposition aluminium alloy of densification, i.e. alloy matrix aluminum.
(6) 316L stainless steel coating is prepared: before spraying, the alloy matrix aluminum obtained step (5) cleans to remove greasy dirt and other dirts of specimen surface, then sandblast machine is utilized to use emergy to carry out sandblasting to aluminium alloy matrix surface, increase surfaceness, improve the bonding strength between 316L stainless steel coating and alloy matrix aluminum.Subsequently, adopt hypersonic flame spraying technology on alloy matrix aluminum, prepare 316L stainless steel coating, the thickness of 316L stainless steel coating is 40.3 μm.The metal-powder of preparation 316L stainless steel coating uses granularity to be 325-330 object 316L powder of stainless steel, spray with propane-oxygen mix burning for thermal source, main technologic parameters is as follows: propane pressure is 0.65Mpa, and flow is 80L/min, oxygen pressure is 1.0Mpa, and flow is 160L/min; Powder particle speed 600m/s in flame gun.
The material property of the aluminium alloy that the present embodiment obtains/316L stainless steel coating matrix material is as shown in table 8 Yu table 9.
The hardness value (HV0.3) of table 8 aluminium alloy/316L stainless steel coating matrix material and bonding strength
The square resistance of table 9 aluminium alloy/316L stainless steel coating matrix material
Alloy matrix aluminum/316L stainless steel coating matrix material prepared by the present embodiment has the following advantages: 1. coating uniform, conducts electricity very well compared with 316L stainless steel, and internal resistance is little many; 2. coating and basal body binding force strong; 3. thermal spray process is convenient, and technique is simple; 4. there is good erosion resistance; 5. coating is fine and close.
Embodiment 5
A kind of aluminium alloy/316L stainless steel coating matrix material, this matrix material comprises alloy matrix aluminum and is sprayed on the 316L stainless steel coating of aluminium alloy matrix surface, and the thickness of 316L stainless steel coating is 59.4 μm; This alloy matrix aluminum material composition comprises: the iron of 10wt%, the mishmetal of 4wt%, and surplus is aluminium and inevitable impurity, is expressed as Al-10Fe-4Re by elementary composition; Wherein Re represents mishmetal.Mishmetal is lanthanum-cerium mishmetal, and composition comprises: La33wt%, Ce63wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity.
The preparation method of above-mentioned aluminium alloy/316L stainless steel coating matrix material, comprises the following steps:
(1) first with fine aluminium ingot and pure iron rod for raw material uses medium-frequency induction furnace melting Al-Fe master alloy, wherein in Al-Fe master alloy, the content of Fe is 20wt%; With fine aluminium ingot and mishmetal for raw material uses well formula crucible electrical resistance furnace melting Al-Re master alloy, Re represents mishmetal, and in Al-Re master alloy, the content of Re is 10wt%;
(2) by the iron of 10wt%, the mishmetal of 4wt%, surplus is the composition proportion of aluminium and inevitable impurity, get fine aluminium ingot, Al-Fe master alloy in medium-frequency induction furnace, Al-Re master alloy is added again after fusing, mix, pour into a mould cooling and demolding afterwards and obtain the aluminium alloy cast ingot comprising 10wt% iron and 4wt% mishmetal;
(3) aluminium alloy cast ingot cleaning: aluminium alloy cast ingot melting obtained is broken, the block alloy of fragmentation is put into successively acetone soln and spirituous solution ultrasonic cleaning, dries stand-by after taking-up;
(4) reaction-injection moulding prepares aluminum alloy round ingot: will clean the block alloy Frequency Induction Heating to 1200 that obtains DEG C ~ 1300 DEG C in step (3), make it melt, then with N
2for atomizing gas, under atomization pressure is 1.5Mpa, reaction-injection moulding prepares Al-10Fe-4Re aluminum alloy round ingot, and detailed process is as follows:
The crucible that the block alloy obtained puts into spray deposition equipment will be cleaned in step (3); wherein crucible uses magnesia crucible; crucible bottom is silicon nitride thrust-augmenting nozzle; draft-tube diameter is 3mm; carry out Frequency Induction Heating to 1300 DEG C to block alloy, block alloy is melted, the melt after thawing is under protection of inert gas; carry out atomization by the thrust-augmenting nozzle coordinated with Double layer non-limited airflow atomizing nozzle separate type to be shaped, atomizing gas is N
2, atomization pressure is 1.5Mpa, and melt mass flow rate in thrust-augmenting nozzle is 1.8kg/min, atomization distance is 500mm, and while atomization, bottom deposit dish rotates with the rotating speed of per minute 120 turns, melt deposition, on bottom deposit dish, obtains Al-10Fe-4Re aluminum alloy round ingot;
(5) hot-pressing densification: hot-pressing densification is carried out to the Al-10Fe-4Re aluminum alloy round ingot that step (4) obtains, the pressuring method of hot-pressing densification is unidirectional pressurization, hot pressing pressure is set to 500Mpa, hot pressing temperature is 350 DEG C, soaking time 2h, obtain the jet deposition Al-10Fe-4Re aluminium alloy of densification, i.e. alloy matrix aluminum.
(6) 316L stainless steel coating is prepared: before spraying, the alloy matrix aluminum obtained step (5) cleans to remove greasy dirt and other dirts of specimen surface, then sandblast machine is utilized to use emergy to carry out sandblasting to aluminium alloy matrix surface, increase surfaceness, improve the bonding strength between 316L stainless steel coating and alloy matrix aluminum.Subsequently, adopt hypersonic flame spraying technology on alloy matrix aluminum, prepare 316L stainless steel coating, the thickness of 316L stainless steel coating is 59.4 μm.The metal-powder of preparation 316L stainless steel coating uses granularity to be 480-500 object 316L powder of stainless steel, spray with propane-oxygen mix burning as thermal source, main technologic parameters is as follows: propane pressure is 0.6-0.7Mpa, flow is 65-100L/min, oxygen pressure is 0.8-1.5Mpa, and flow is 150-170L/min; Powder particle speed 550-650m/s in flame gun.
The material property of the aluminium alloy that the present embodiment obtains/316L stainless steel coating matrix material is as shown in table 10 Yu table 11.
The hardness value (HV0.3) of table 10 aluminium alloy/316L stainless steel coating matrix material and bonding strength
The square resistance of table 11 aluminium alloy/316L stainless steel coating matrix material
Alloy matrix aluminum/316L stainless steel coating matrix material prepared by the present embodiment has the following advantages: 1. coating uniform, conducts electricity very well compared with 316L stainless steel, and internal resistance is little many; 2. coating and basal body binding force strong; 3. thermal spray process is convenient, and technique is simple; 4. there is good erosion resistance; 5. coating is fine and close.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. aluminium alloy/316L stainless steel coating matrix material, is characterized in that, this matrix material comprises alloy matrix aluminum and is sprayed on the 316L stainless steel coating of aluminium alloy matrix surface; Wherein the thickness of 316L stainless steel coating is 40 ~ 60 μm;
Described alloy matrix aluminum material composition comprises: the iron of 6 ~ 10wt%, the mishmetal of 2 ~ 6wt%, and surplus is aluminium and inevitable impurity;
Described mishmetal is lanthanum-cerium mishmetal, and composition comprises: La32 ~ 33wt%, Ce62 ~ 63wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity.
2. a kind of aluminium alloy according to claim 1/316L stainless steel coating matrix material, is characterized in that, described alloy matrix aluminum material comprises: the iron of 8wt%, the mishmetal of 4wt%, and surplus is aluminium and inevitable impurity.
3. a kind of aluminium alloy according to claim 1/316L stainless steel coating matrix material, it is characterized in that, described mishmetal composition comprises: La32.6wt%, Ce62.6wt%, O1.6wt%, F0.3wt%, Fe0.54wt%, Al0.39wt%, Mg0.24wt%, P0.17wt%, Cl0.16wt%, Zn0.12wt% and inevitably impurity.
4. a preparation method for aluminium alloy as claimed in claim 1/316L stainless steel coating matrix material, it is characterized in that, the method comprises the following steps:
(1) with fine aluminium ingot and pure iron rod for raw material melting Al-Fe master alloy, wherein in Al-Fe master alloy, the content of Fe is 20wt%; With fine aluminium ingot and mishmetal for raw material melting Al-Re master alloy, Re represents mishmetal, and in Al-Re master alloy, the content of Re is 10wt%;
(2) get fine aluminium ingot, Al-Fe master alloy in medium-frequency induction furnace, add Al-Re master alloy again after fusing, mix, pour into a mould cooling and demolding afterwards and obtain the aluminium alloy cast ingot comprising 6 ~ 10wt% iron and 2 ~ 6wt% mishmetal;
(3) aluminium alloy cast ingot cleaning: aluminium alloy cast ingot melting obtained is broken, the block alloy of fragmentation is put into successively acetone soln and spirituous solution ultrasonic cleaning, dries stand-by after taking-up;
(4) reaction-injection moulding prepares aluminum alloy round ingot: by cleaning block alloy Frequency Induction Heating to 1100 ~ 1300 DEG C obtained in step (3), make it melt, then with N
2for atomizing gas, under atomization pressure is 0.8 ~ 1.5Mpa, reaction-injection moulding prepares aluminum alloy round ingot;
(5) hot-pressing densification: carry out hot-pressing densification to the aluminum alloy round ingot that step (4) obtains, obtains the jet deposition aluminium alloy of densification, i.e. alloy matrix aluminum;
(6) 316L stainless steel coating is prepared: adopt hypersonic flame spraying technology on alloy matrix aluminum, prepare 316L stainless steel coating, obtain aluminium alloy/316L stainless steel coating matrix material.
5. the preparation method of a kind of aluminium alloy according to claim 4/316L stainless steel coating matrix material, it is characterized in that, fine aluminium ingot described in step (1) is the technical grade aluminium ingot that purity is not less than 99.95wt%, described pure iron rod for diameter that iron level is not less than 99.99wt% be the technical pure iron staff of 5mm, described mishmetal is lanthanum-cerium mishmetal, composition comprises: La32 ~ 33wt%, Ce62 ~ 63wt%, and remainder is F, Fe, Al, Mg, P, Cl, Zn and inevitable impurity.
6. the preparation method of a kind of aluminium alloy according to claim 4/316L stainless steel coating matrix material, is characterized in that, the detailed process that the middle reaction-injection moulding of step (4) prepares aluminum alloy round ingot is as follows:
The crucible that the block alloy obtained puts into spray deposition equipment will be cleaned in step (3); wherein crucible uses magnesia crucible; crucible bottom is silicon nitride thrust-augmenting nozzle; to block alloy carry out Frequency Induction Heating to 1100 ~ 1300 DEG C; block alloy is melted; melt after thawing, under protection of inert gas, carries out atomization by the thrust-augmenting nozzle coordinated with Double layer non-limited airflow atomizing nozzle separate type and is shaped, and atomizing gas is N
2, atomization pressure is 0.8 ~ 1.5Mpa, and melt mass flow rate in thrust-augmenting nozzle is 1.7 ~ 1.8kg/min, atomization distance is 400 ~ 500mm, and while atomization, bottom deposit dish rotates with the rotating speed of per minute 45 ~ 120 turns, melt deposition, on bottom deposit dish, obtains aluminum alloy round ingot.
7. the preparation method of a kind of aluminium alloy according to claim 4/316L stainless steel coating matrix material, it is characterized in that, in step (5), the pressuring method of hot-pressing densification is unidirectional pressurization, hot pressing pressure is set to 300 ~ 500Mpa, hot pressing temperature is 250 ~ 350 DEG C, soaking time 1 ~ 2h.
8. the preparation method of a kind of aluminium alloy according to claim 4/316L stainless steel coating matrix material, it is characterized in that, in step (6), the metal-powder of preparation 316L stainless steel coating uses granularity to be 325 ~ 500 object 316L powder of stainless steel, spray with propane-oxygen mix burning as thermal source, main technologic parameters is as follows: propane pressure is 0.6 ~ 0.7Mpa, flow is 65 ~ 100L/min, and oxygen pressure is 0.8 ~ 1.5Mpa, and flow is 150 ~ 170L/min; Powder particle speed 550 ~ 650m/s in flame gun.
9. the preparation method of a kind of aluminium alloy according to claim 4/316L stainless steel coating matrix material, is characterized in that, before preparation 316L stainless steel coating, carry out surface treatment to alloy matrix aluminum, method is as follows:
First the greasy dirt and other dirts that remove surface are cleaned to alloy matrix aluminum, then sandblast machine is utilized to use emergy to carry out sandblasting to aluminium alloy matrix surface, increase surfaceness, improve the bonding strength between 316L stainless steel coating and alloy matrix aluminum.
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