CN100464004C - Target pole for coating and its casting process for external sleeve - Google Patents
Target pole for coating and its casting process for external sleeve Download PDFInfo
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- CN100464004C CN100464004C CNB2005100469015A CN200510046901A CN100464004C CN 100464004 C CN100464004 C CN 100464004C CN B2005100469015 A CNB2005100469015 A CN B2005100469015A CN 200510046901 A CN200510046901 A CN 200510046901A CN 100464004 C CN100464004 C CN 100464004C
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Abstract
A target pole used for coating mainly consists of outer casing and inner casing, wherein inner casing installed in outer casing and fixed joint, outer casing made of aluminium as base material, the other composition percentage composition: Si 4.5-5.5 per cent, Y 1.1-1.8 per cent. An above-mentioned coating used target pole outer casing casting technique is casting, said target pole raw material: industry pure aluminium, industry silicon, Al -Y intermediate alloy, said target pole outer casing casting process: firstly smelting raw material, cast moulding in metal mould. Said invented target pole application effect in coating is obviously better than current technology with high cast product quality.
Description
Technical field:
The present invention relates to Materials science, a kind of casting technique of overcoat of target pole for coating is provided especially.
Background technology:
Target pole for coating is used to apply strength member as a kind of important volatilization cathode material, with high-temperature oxidation resistant, the corrosion resistance of raising workpiece surface, thereby improves its use properties.
Target pole material of the prior art is single layer structure normally.For double-deck target pole for coating, usually its overcoat is the vital part as the volatilization negative electrode, interior cover is the part that waits other secondary purpose as cooling, forms a fixed connection usually between overcoat and the interior cover, and fixedly connected quality directly affects the quality of the target utmost point and coating.
Therefore, people expect to obtain better target pole for coating material of a kind of effect and corresponding manufacturing process thereof, so that obtain better technique effect.
Summary of the invention:
Target pole for coating of the present invention, the correlation technique division is as follows:
One, the target utmost point is formed:
Described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, is fixedly connected between the two; Described overcoat (1) is the vital part that is used as the volatilization negative electrode when carrying out coating operation; Overcoat (1) is selected the Al sill for use, and according to weight percent, other composition quality degree except that Al is: Si:4.5～5.5%; Y:1.1～1.8%; Require other composition Fe≤0.25% for example in the lagging material under the optimum condition.
Interior cover (2) is a watercooling jacket, requires the material densification, and thermal conductivity is good; It can interior cover (2) be a watercooling jacket in the preferred version, requires the material densification, and thermal conductivity is good; It can select the A1 sill for use in the preferred version, and according to weight percent, other component content except that A1 is: Cu:3.8～4.9%; Mn:0.3～0.9%; Mg:1.2～1.8%; Si≤0.5%; Fe≤0.5%; Zn≤0.3%; Ni≤0.1%;
Described overcoat (1) and interior cover (2) form of fixedlying connected between the two is preferably soldering.Soldering selects for use scolder to be preferably the Pb sill, and one of preferred concrete example is: according to weight percent, other component content except that Pb is: Sn:38～42%; Sb:1.3～2.3%; Impurity≤0.5%.
Gap between described overcoat (1) and the interior cover (2) be 0.3～2mm (be preferably 0.8～1mm), described gap is filled up with scolder behind brazing operation, thus the thickness of brazing layer (3) promptly corresponding above gap width.The scantlings of the structure of the described target utmost point is preferably as follows: overcoat thickness is 5～40mm (preferred 10～30mm); Interior cover thickness is 1～20mm (preferred 2～8mm);
Two, target utmost point manufacturing process
One) overcoat manufacturing process
The overcoat of target pole for coating (1) can be cast member.
Target utmost point lagging material is the Al-Si-Y alloy of casting.The outer Y of the applying mechanically master alloy of smelting the negative electrode target can adopt vacuum induction melting; External sleeve blank can adopt the method manufacturing of permanent mold casting, bottom pouring type pouring.Few people carry out the research work of this alloy at present, also not having relevant standard and data can look into, simultaneously, according to the working order of the target utmost point, as the necessary densification of volatilization negative electrode requirement material itself, no nonmetal inclusion, pore, shrinkage cavity, loose, pin hole etc. influence the defective of electroconductibility, with the continuity that guarantees to apply, high to the quality control requirement of castingprocesses, so the casting technique of lagging material Al-Si-Y alloy is one of gordian technique in the present technique.
The casting technique of the overcoat of target pole material (1):
The overcoat of described target pole for coating material (1) selects for use following starting material to make: commercial-purity aluminium, industrial silicon, Al-Y master alloy; The castingprocesses of described overcoat (1) is: at first melting starting material, casting in metal die (4) then.
The overcoat of described target pole for coating material (1) can select for use following starting material to make: commercial-purity aluminium, industrial silicon, Al-Y master alloy; It preferably can be following scheme that described raw material is formed according to weight percent: the content composition of industrial silicon is: Si is about 99%, and Fe is about 0.3%, and Al is about 0.3%, and Ca is about 0.05%; The content composition of Al-Y master alloy is: Y is about 10%, Fe≤0.15%, other impurity summation≤0.5%.
Metal die (4) mainly is made up of metal inner core (401), metal die overcoat (402) and metal bed die (403); Wherein metal inner core (401) and metal die overcoat (402) all cooperate installation with metal bed die (403), and metal inner core (401) is installed in metal die overcoat (402) inside.That matches with metal die (2) can also have sand mold loam cake (5) and sprue cup (6).
The casting technique of described target pole for coating overcoat (1) is divided into raw material melting and cast two big steps:
Described melting technology is: select for use electrical crucible as melting equipment, at first with the crucible preheating, put into the melting raw material then and carry out melting.
Preferred starting material melting technology is in the casting technique of target pole for coating overcoat (1): select electrical crucible for use; Should clear up crucible before using, guarantee in the crucible and no any other material in surface; Further preferably by following requirement batching: Y prepares burden by about 1.8%, uses Al-Y alloy (Y10%) batching, and (estimate that alloy scaling loss amount is: Si is about 0.5% to Si by about 5% batching; Y is about 1.0%); Can at first electrical crucible be preheating to 200～400 ℃ during melting, add commercial-purity aluminium and Al-Y master alloy then, it is clear to be warming up to wholeization of furnace charge, and solution temperature to 550 in the adjustment stove～800 ℃, add industrial silicon then, close bell to industrial silicon and melt fully, and can add insulating covering agent; Refining then, and can stir and make the alloy homogenizing; (removing insulating covering agent) also adds the degasifier degasification, removes alloy liquid surface slag afterwards.
In the casting technique of target pole for coating overcoat (1), described preferred melting technology is: described electrical crucible is a plumbago crucible, plumbago crucible is preheating to 250～350 ℃, add commercial-purity aluminium and Al-Y master alloy then, it is clear to be warming up to wholeization of furnace charge, and solution temperature to 650 in the adjustment stove～750 ℃, add industrial silicon then, close bell to industrial silicon and melt fully; Alloy liquid surface slag is removed in refining under the condition that guarantees alloy liquid homogenizing then; Add the hexachloroethane degasification, add-on is 0.1%～2% of an alloy total amount.
Described pouring technology is: at first with metal die (4) preheating, and assembling die and cast as requested then.Described preferred pouring technology can be: at first metal die (4) is preheating to 250～550 ℃ and the insulation until metal die (4) everywhere temperature evenly pour into a mould again; Casting process can be: open bell, remove surface scale; Contain out alloy liquid, treat to pour into a mould when the alloy liquid temp is 650～800 ℃ in the casting ladle, metal die when pouring into a mould simultaneously (4) temperature should be controlled between 200～350 ℃; After treating that casting pressing port solidifies, opening metal mould (4) takes out overcoat (1).
Described pouring technology preferably can be: before building, go up graphite spraying coating at the metal inner core (401) of metal die (4) earlier, go up the spraying zinc oxide coating at metal die overcoat (402), above-mentioned coating layer required thickness is even, and total coating thickness is no more than 0.4mm; The coating of clearing up metal die (4) surface dirt then and adhering to makes up metal die (4) then, prepares cast; The cast instrument of all uses should spray zinc oxide coating, and is heated to (preferred 350～600 ℃) more than 350 ℃, reduces to room temperature then and uses.
Preferred casting process is: earlier metal die (4) is heated to 380～420 ℃ in stove, and is incubated more than 0.5 hour; At first remove surface scale after opening bell, contain out alloy liquid with the exsiccant casting ladle then, carry out thermometric, cast when the alloy liquid temp is 700～750 ℃ in waiting to wrap, metal die when pouring into a mould simultaneously (4) temperature should be controlled between 230～320 ℃; After treating that casting pressing port solidifies, opening metal mould (4) takes out overcoat (1).
The advantage of the casting technique of the above target pole for coating overcoat is: at novel target pole for coating, processing method of the present invention is workable, effective, simple and practical, has great promotion and application and is worth.
Other associated problem researchs in the overcoat casting technique:
1, the preparation of aluminium yttrium master alloy
The fusing point of metallic yttrium is 1450 ℃, and density is 6.07, and crystal formation is a close-packed hexagonal; 660 ℃ of the fusing point of metallic aluminium, density is 2.7, crystal formation is a face-centered cubic, because the changing of the relative positions of face-centered cubic lattice meta can be less, easily produce dislocation, and dislocation provides passage for ion moves in matrix, therefore the Y ion can be spread in the Al matrix, according to the Al-Y alloy phase diagram, basic available scope is in the practical application: Y atomic molar ratio 2～5% (weight percent 6～20%), and this moment, alloy liquid phase line temperature was about about 620～660 ℃; Referring to Fig. 3, preferred data are: the Y atomic molar ratio is when 2.8% (weight percent 10%) left and right sides, can form eutectic, more help the melting of next step alloy, this moment, alloy liquid phase line temperature was at about about 640 ℃, thus we preferably the Y weight percent be about 10% Al-Y alloy master alloy as melting.
Because yttrium is extremely active, very easily oxidation in atmosphere, simultaneously under the high temperature, chemical reaction all takes place in yttrium and general oxide refractories, so we select for use the water jacketed copper crucible vacuum induction furnace to carry out the preparation of aluminium yttrium master alloy.By test of many times, definite blending process is as follows: add rafifinal and pure yttrium in proportion in crucible, vacuumize, when vacuum tightness reaches about 2 * 10
-1Send electricity during Pa, controlled temperature is at about about 900 ℃ (± 20 ℃), treat that alloy melts fully after, be cooled to (± 20 ℃) about 700 ℃.And then send electricity, and making homogenization of composition by function composite by electromagnetic stirring, and be cast in rapidly in the ingot mold, cooling back vacuum breaker takes out, and is stored in the sealing bore stand-by.
After operating according to above preferred parameter, through chemical analysis, the concrete composition of master alloy is as follows: Y is about 10.01%; Fe is about 0.079%; Al is a matrix metal.
2, the quality control of overcoat (1)
1) overcoat (1) after casting is finished carries out X-ray examination, acceptable defect level(ADL) should meet I class foundry goods regulation among the GB9438-88, the inner no any defective of foundry goods, conform to the requirement of A level (superlative degree) foundry goods in the U.S. AA-CS-M5-85 aluminum alloy casting split pole standard, X-ray check can adopt U.S. ASTM E-155 aluminium, Mg alloy castings non-destructive testing standard.
2) foundry goods is after mechanical workout, and finished surface does not have any defective.
3) the foundry goods body sampling carries out chemical composition analysis, and the result in certain test is as follows:
Top: Y 1.58%; Si 4.55%; Fe 0.15%
Middle part: Y 1.52%; Si 4.47%; Fe 0.13%
Bottom: Y 1.61%; Si 4.35%; Fe 0.16%
By chemical composition analysis as can be known, the overcoat of cast form (1) composition is even.In addition, because the Al-Y master alloy is just coated by aluminium liquid after entering aluminium liquid at once, can't contact with air, simultaneously owing to the effect and the alloy temperature of insulating covering agent are controlled, so the scaling loss of alloying element Y is very little.
Chemical analysis method is got one by the every stove of GB/T6987-86 and is carried out, and provides chip by the supplier by heat (batch) number.If when chemico-analytic result is defective for the first time, allow to carry out the chemical analysis second time.When the second time, chemico-analytic result was still defective, then each part is carried out chemical analysis.
4) we carry out scanning electron microscope analysis to the foundry goods body, electronic microscope photos result such as accompanying drawing 4～6.From accompanying drawing 4～6 as can be seen, yttrium form and distribution basically identical in two kinds of foundry goods, and all more even.Homemade the content owing to Y is higher, so distribution density is bigger.In addition, in the distribution of silicon, except that primary silicon, have the silicon-yttrium coexisting phase that is evenly distributed in the matrix, from Fig. 7 Y-Si Phase Diagram Analysis, this may be the mixture of Y3Si5 and Al3Y mutually, hence one can see that, Y has the Si effect of crystals growth just that hinders, and therefore exists in the situation with alterant not, and primary silicon is also more tiny.By above analysis as can be known, aluminium yittrium alloy overcoat casting quality excellence, alloying constituent is even, and interior tissue is functional.
The supply status of target pole material before the soldering of casting back: after the cathode targets mechanical workout that provides without the thermal treatment supply.
Two) manufacture craft of the interior cover (2) of the target utmost point
Interior cover is watercooling jacket, requires the material densification, and thermal conductivity is good, learns by chemical analysis, and its chemical ingredients is the LY12 alloy, therefore selects for use the LY12 hard aluminium alloy bar material can satisfy service requirements fully through mechanical workout.Interior cover adopts LY12 aluminium alloy manufacturing (can be casting), and chemical ingredients should meet the requirement of GB3191-82.
Cover (2) is selected the Al sill for use particularly, and according to weight percent, other component content except that Al is: Cu:3.8～4.9%; Mn:0.3～0.9%; Mg:1.2～1.8%; Si≤0.5%; Fe≤0.5%; Zn≤0.3%; Ni≤0.1%;
Three) overcoat of the target utmost point (1) and interior cover (2) the fixedly connected mode preferred version between the two is to adopt the soldering processes fixed.Soldering processes between overcoat (1) and the interior cover (2) are one of gordian techniquies of the present invention, for guaranteeing the works fine state of target utmost point overcoat (1), brazing layer (3) between overcoat (1) and the interior cover (2) must have good heat conduction and conductivity, simultaneously necessary between brazing layer (3) and overcoat (1) and the interior cover (2) in conjunction with tight, very close to each other, otherwise, during the work of the target utmost point, under the effect of big electric current, gap location can produce superheating phenomenon, cause the local material fusing, thereby cause operational failure.Gap between the interior overcoat (filled up by brazing layer (3), described gap width just corresponding the thickness of brazing layer (3)) be that 0.3～2mm (is preferably 0.8～1mm), therefore will obtains good soldering effect, just must have high-quality soldering processes to guarantee.
Described overcoat (1) and interior cover (2) between the two soldering select for use scolder to be preferably the Pb sill, it is as follows preferably to form proportioning: according to weight percent, the quality percentage composition of other composition except that Pb is: Sn:38～42%; Sb:1.3～2.3%; Impurity≤0.5%.
The chemical ingredients (%) of the preferred braze of table 1
| Element | Sn | Sb | Pb | Cu | As | S | Fe | Zn | Ni | Al |
| Content | 39- 41 | 1.5- 2.0 | Matrix | ≤ 0.08 | ≤ 0.05 | ≤ 0.02 | ≤ 0.05 | ≤ 0.002 | ≤ 0.1 | ≤ 0.005 |
By above one-tenth assignment system braze and fusing, pour into band sample after stirring and carry out chemical composition analysis and Milling Process with the homogeneity of checking composition and the compactness of material, measure fusing point, its fusing point is 280 ℃, its chemical ingredients sees Table 2.
Table 2 braze chemical ingredients
As shown in Table 2, the composition of this braze is even and scaling loss is few.Because the density of this braze is too big, can't check its inner quality by the X-ray, so we are by being the depth of cut with 0.5mm to sample, successively carry out Milling Process, and observing finished surface with magnifying glass, the result does not find any defective, illustrates that the internal soundness of braze is very fine and close.
A kind of target pole material soldering process for coating layer, soldering raw material are selected technical pure lead, industrial pure tin and industrial star antimony for use; Melting unit is temperature automatically controlled resistance furnace, plumbago crucible and baking oven; The two process of carrying out soldering of described overcoat (1) and interior cover (2) is: at first to overcoat (1) and interior cover (2) carry out surface activation process with reduce between scolder and the overcoat (1) and scolder and interior cover (2) between angle of wetting, then they are installed on the solderer and load onto the enforcement brazing operation.
The research of the surface activating process of target pole material:
(preferably has only 0.8mm～1mm) because overcoat (1) and interior cover (2) gap between the two is very little, therefore for guaranteeing brazing quality, require the wetting angle of scolder and interior overcoat the smaller the better, preferably lining the outer surface of and overcoat internal surface are carried out surface activation process in advance.
Because the wetting angle of metallic tin and scolder (Pb, Sn, Sb alloy) is 0, but complete wetting, therefore we have selected overcoat (1) and interior cover (2) electroplating surfaces with tin, but because the bonding force between tin and the aluminum substrate is little, poor permeability, so adopted elder generation in the copper facing of A1 matrix surface, then at the recombining process of copper electroplating surfaces with tin.Finally, use this technology to plate one deck preferred thickness uniformly at the internal surface of the outside surface of interior cover (2) and overcoat (1) and be about the copper coating of 5-8 μ m and plate one deck preferred thickness on the copper coating surface and be about 10-15 μ m, compact tin coating is seen Fig. 8.
Target pole for coating material soldering skill process is: will be in advance through the sealing that is installed of the overcoat (1) of the target utmost point of surface activation process and interior cover (2), put it into then in the baking oven, under 230～350 ℃ of conditions, be incubated at least 0.5 hour; Melting solder melts Pb under 350～450 ℃ of conditions then, adds Sn, Sb then successively, stirs after the fusing fully, and is incubated under 270～390 ℃ of conditions; Target utmost point assembly and scolder that said process was handled carry out soldering cast, 230～350 ℃ of preheating temperatures, 270～390 ℃ of pouring temperatures simultaneously; Behind the casting complete, cooling sheds jig.
Target pole for coating material soldering skill preferred content is: will be in advance through the sealing that is installed of the overcoat (1) of the target utmost point of surface activation process and interior cover (2), put it into then in the baking oven, under 280～300 ℃ of conditions, be incubated at least 1～4 hours; Melting solder melts Pb under 350～450 ℃ of conditions then, adds Sn, Sb then successively, stirs after the fusing fully, and is incubated under 270～390 ℃ of conditions; Target utmost point assembly (overcoat (1) and the interior cover (2) that comprise the target utmost point) and scolder that said process was handled carry out soldering cast, 280～300 ℃ of preheating temperatures, 320～340 ℃ of pouring temperatures simultaneously.
Target pole material soldering process for coating layer, it is characterized in that: adopt special tooling (8) to be used for the overcoat (1) of the target utmost point and interior cover (2) are installed and seal, the structure of described special tooling (3) mainly is that the following components formation is arranged: firm banking (801), holding bolt (802), sprue cup (803); For ease of the location of the installation before the soldering, can also select gap pin (804) for use.
Target pole material soldering process for coating layer of the present invention is characterized in that: before soldering to the overcoat (1) of the target utmost point and the surface activation process of interior cover (2) be: the overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and interior cover (2) surface portion carries out copper plating treatment and carry out zinc-plated processing again on the copper surface.
The research of chemical-copper-plating process:
1) the coating principle of novel process electroless copper: the same with other general chemical-copper-plating process, novel process is to make the cupric ion of the free state in the copper electrolyte be reduced into a kind of method that solid-state copper crystal is coated in workpiece surface by the reductive agent (inferior sodium phosphate) that is fit to.
2) thermodynamic condition of electroless copper:
Electroless copper occurs in the aqueous solution and the solid interface with catalytic activity, by reductive agent cupric ion is reduced into metal copper layer.Chemical equation is in the plating bath:
Cu
2++NaH
2PO
2+3OH→Cu+NaH
2PO
2+2H
2O
E
0＝Ψ
0Cu
2+/Cu-Ψ
0NaH
2PO
2/NaH
2PO
2
Because the current potential of inferior sodium phosphate is more negative than the current potential of cupric ion, so judge from thermodynamics, is feasible with ortho phosphorous acid sodium reduction cupric ion.
People wish that the reaction of electroless copper only occurs in workpiece surface, and still, from thermodynamics, the electroless copper system is unsettled in essence.If have activation core, impurity or some metal particle, just may cause in the solution body, redox reaction taking place at any time.The complexing agent of normal concentration can not stop the spontaneous decomposition of plating bath, for preventing this problem, must add stablizer in the plating bath.The add-on of stablizer is very little, and they are preferentially adsorbed on the activity core surface and stop itself and reductive agent to react; If the stablizer add-on is too much, electroless copper may stop fully.
Sometimes add in the plating bath after the complexing agent, plating speed is very slow, and adding certain additive increases plating speed to proper level, is unlikely to damage the stability of plating bath again, and this class additive is referred to as promotor.
In a word, in the aqueous solution, do reductive agent reduction cupric ion and satisfy thermodynamic condition with inferior sodium phosphate.Favourable to the electroless copper reaction in basic solution, but suitable complexing agent, buffer reagent and stablizer must be contained in the plating bath.
3) kinetics of electroless copper:
Setting up on thermodynamics, chemical reaction also must satisfy dynamic conditions.Electroless copper needs heat energy that reaction is carried out as other catalyzed reaction, and this is the reason that chemical plating fluid just has plating speed when reaching certain temperature.The speed of electroless copper can be expressed with the minimizing of reaction product concentration increase and reactant concn in theory.Owing to contain some additive in the actual chemical bronze plating liquid that uses, so that stablize plating bath and improve coating performance.But the existence of these additives makes influence factor too much, so situation becomes quite complicated.The scientific worker has proposed mechanism, the hypothesis of various electroless platings, attempts the experimental fact of electroless copper is made proper explanations, increases the understanding to the essence of electroless copper phenomenon.The comprehensive former achievements of this problem according to the experiment data of surveying, proposes following kinetic model:
The electroless copper cathodic reaction is that the possibility of cupric ion reduction course is as follows:
[CuEDTA]
2-+e
-＝Cu
0+EDTA
4- (A)
The Tafel slope of the polarization curve of cathode portion is-163.5mv/dec.Need very high activation energy based on the bielectron transition, so mechanism (A) is excluded.For mechanism (C), be not inconsistent with the actual measurement electrochemical parameter, can not set up.Therefore the reduction course of cupric ion only may be undertaken by mechanism (B).Be the transition of bielectron substep;
Step is the speed control link of cathodic reaction.
H
2PO
2 -+H
2O＝H
2PO
3 -+H
++2H
ad (D)
Above-mentioned being reflected in the copper deposition process all taken place simultaneously, and single speed of response then is decided by conditions such as plating bath composition, life cycle, temperature and pH value.
Tin plating technique research:
After the surfaces externally and internally of target pole material applies one deck conductive copper, in order to make coating and braze (pewter, 280 ℃ of fusing points) the excellent wetting capacity energy is arranged, in the substrate of copper coating, hang up one deck tin again, traditional tining technology is manual tining, the shortcoming of this technology maximum is that the tin layer is inhomogeneous, (only has 0.8～1mm) usually, uses manual method obviously not all right because the gap is very little between overcoat (1) and the interior cover (2).
The overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and the process that interior cover (2) surface portion carries out copper plating treatment are successively: degreasing, soak heavy ion, strip, electroless copper, wherein: the degreasing formation of filling a prescription is: OP emulsifying agent, Na
2CO
3, NaPO
3According to mass percent, Na wherein
2CO
3Be 10～30%, NaP0
3: 5～25%; The degreasing process standard is: temperature: 40～80 ℃, and the time: 5～60min;
Soaking heavy ion prescription formation is: composite additive, Ni
2-, CO
2+Wherein, Ni
2+, CO
2+: 30～70g/L; Soaking the heavy ion technological specification is: temperature: 15～30 ℃, and the time: 1～10min;
The decoating liquid prescription is: chromic acid: 4～18g/L, HCL:2～12g/L; The withdrawal plating standard is: temperature: 15～30 ℃, and time 1～2min.
The solution composition of electroless copper and characteristic: the chemical bronze plating liquid main component of novel process has: mantoquita, complexing agent, reductive agent, pH value are adjusted agent, are separated out promotor, trace mineral supplement, solution stabilizer etc.
The prescription of electroless copper is: CuSO
45H
2O:60～90g/L; EDTA:80～150g/L; NaH
2PO
2H
2O:20～80g/L; Cl, β γ: 30～60g/L; Ni
2+, Co
2+: 0.1～10g/L; 2-MBT:0.1～10g/L; 1,1-dipyridyl: 1～20mg/L; The chemical-copper-plating process standard is: pH:9～12; Temperature: 60～70 ℃; Plating speed: 8～10 μ m/h; Time: 60～100min.
The overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and the preferred process that interior cover (2) surface portion carries out copper plating treatment are successively: degreasing, wash, soak heavy ion, strip, washing, electroless copper, washing, drying, wherein, water washing process is for adopting the washing of deionized water room temperature, and the time is preferably 1～5min.
Copper coating composition and morphological analysis: copper coating mainly contains compositions such as Cu, Ni, P, Co under this technology, and inferior sodium phosphate is as the reductive agent of electroless copper.Ni
2+The change of concentration is listed in table 3 to the influence of Ni/Cu ratio and resistance value in coating speed of separating out, the coating.As known from Table 3, increase Ni in the plating bath
2+Concentration promptly improves Ni in the coating, the content of P, and Ni/Cu ratio is lower than Ni in the plating bath in the coating
2+/ Cu
2+Ratio, thereby Cu in the plating bath
2+Easier being reduced.In addition, Ni/Cu ratio is directly proportional with resistance value in the coating, and the promotor of separating out of additive is Co sometimes
2+Rather than Ni
2+, Co/Cu is lower than and adds Ni in this case
2+The time coating in Ni/Cu ratio.
Table 3 Ni
2-Concentration is to the influence of Ni/Cu ratio and resistance value in coating speed of separating out, the coating
| Cu 2+Concentration/molL -1 | Ni 2+Concentration/molL -1 | Ni 2+/Cu 2+/mol％ | Coating speed of separating out/um/20min | Ni/Cu/mol in the coating | Coating resistance value/μ Ω cm -1 |
| 0.0240 | 0.0020 | 7.7 | 1.76 | 3.0 | 17 |
| 0.0300 | 0.0025 | 7.7 | 2.95 | 4.6 | 19 |
| 0.0240 | 0.0055 | 18.6 | 2.48 | 7.7 | 25 |
| 0.0300 | 0.0069 | 18.7 | 3.63 | 7.0 | 20 |
| 0.0100 | 0.0030 | 23.1 | 1.03 | 9.8 | 92 |
| 0.0200 | 0.0050 | 20.0 | 2.21 | 8.7 | 40 |
| 0.0500 | 0.0040 | 44.4 | 0.44 | 25.0 | 410 |
| 0.0150 | 0.0100 | 40.0 | 2.14 | 17.7 | 66 |
| 0.025 | 0.0045 | 64.3 | 0.27 | 46.3 | 1100 |
| 0.0100 | 0.0150 | 60.0 | 1.54 | 33.0 | 248 |
| 0 | 0.0250 | 100.0 | 0.33 | 100 | 1980 |
| 0 | 0.0050 | 100.0 | 0.15 | 100 | 4000 |
General chemical plating copper layer configuration of surface is quite coarse, and forms granular crystal easily, if but increase Ni in the plating bath
2+Concentration, rising pH value, and adopt inferior sodium phosphate as reductive agent, the configuration of surface of copper plate just has significantly to be improved.Obtainable coating is level and smooth, crystal grain is tiny, increase with the adsorptive power of target pole material.Tensio-active agents such as adding thiocarbamide, 2-MBT can obtain the copper coating of needle crystal, and this is that other electroless copper method is incomparable.
Binding force of cladding material is analyzed: binding force of cladding material is meant the bonding strength of coating and matrix metal (or intermediate deposit), and promptly the coating of per surface area is peeled off needed power from matrix metal (or intermediate deposit), is one of important mechanical property of coating.The bad meeting of binding force of cladding material causes plating exfoliation, not only directly influences visual appearance, and the protective of coating and functional (as conduction, wear-resisting, weldability etc.), so binding force of cladding material is defective, then need not carry out the check of other performance.
Bonding force at target pole material (especially aluminium yittrium alloy) copper facing coating is very poor, adopts general secondary soaking zinc method can't meet the demands at all.For this this problem adopts up-to-date dip-coating prescription-soak heavy ion prescription.Before electroless copper, to target pole material dip-coating heavy ion, make the target pole material surface active after the stripping, so that obtain good bonding force.
Target pole material after adopting the thermal shock method to copper facing is tested, and is about to target pole material and is heated to about 600 ℃, and insulation 1～1.5h takes out the back shrend, and copper coating does not peel off, and this explanation is good by the copper coating bonding force that this technology obtained.
Target pole for coating material soldering skill preferred content: the overcoat (1) and interior cover (2) surface portion of the target utmost point that brazing solder can touch during to the enforcement soldering carry out zinc-plated processing:
Chemical tin plating process research:
Described target pole material soldering process for coating layer is characterized in that: the overcoat (1) of the target utmost point that brazing solder can touch during to the enforcement soldering and interior cover (2) surface portion carry out after the copper plating treatment and carry out chemical wicking before the zinc-plated processing and handle.
Wicking is workpiece to be immersed contain in the solution of tin metal salt, deposits the metallic tin layer by the chemical replacement principle at workpiece surface.It is different with general electroless plating principle, does not contain reductive agent in the wicking liquid.Current potential (the E of copper
0Cu
2+/ Cu=0.34v) than tin (E
0Sn
2+/ Sn=-0.14v) just, thereby judge from thermodynamic principles and from copper plate, can not displace tin, promptly can not realize wicking.Be implemented in the copper plate immersion tin and must add copper ion complexing agent, as thiocarbamide, citric acid, prussiate etc.They and Cu
2+Form negative significantly the moving of current potential that stable comple makes copper later on.When the concentration of complexing agent reached certain numerical value, replacement(metathesis)reaction can take place, and deposited tin on copper coating.Experiment shows that concentration is about thiourea concentration the best of 2.0mol/L, and this replacement(metathesis)reaction can be write as: Sn
2++ Cu N
2H
4CS → Sn ↓+Cu
2+The effect that thiocarbamide improves quality of coating in addition, improves bonding force.
Two side reactions take place in the wicking process make Cu
2-Increase Cu
2+Gathering can influence the weldability of bath life and coating, therefore should avoid the oxygenizement of air to Cu as far as possible
2Cu+O
2＝2CuO
And Cu
2+Dissolving to Cu
Cu
2++Cu＝2Cu
+
Described prescription and the technological specification that on copper coating, carries out chemical wicking: Sn
2+: 10～20g/L; HCl:10～20g/L; N
2H
4CS:35～50g/L; Temperature: 50～80 ℃; Time: 1～2min.
The shortcoming of chemistry wicking method be can only be on copper plate the limited tin layer (0.5 μ m generally only has an appointment) of deposit thickness, for this reason must be on the wicking layer chemical plating stannum.
This process using reductive agent forensic chemistry is zinc-plated, and detailed process is: select following prescription: SnCl for use
2: 3～15g/L, Trisodium Citrate: 50～150g/L, EDTA disodium: 5～30g/L, NaCH
3COO:5～20g/L, TiCl
3: 5～25ml/L, Phenylsulfonic acid: 0.2～5ml/L; Processing parameter is as follows: pH:8.0～10.0, temperature: 70～130 ℃.
Trisodium Citrate is Sn in the plating bath
2+Complexing agent, concentration is greater than 120g/L, it is low then to plate prompt drop, and less than 80g/L plating bath instability, is the best with about 100g/L.The EDTA disodium stops Ti
3+Oxidation, its influence is identical with Citrate trianion, and concentration is crossed low too high all bad, is advisable with about 15g/L.NaAC is little to the sedimentation velocity influence, but helps improving the stability of plating bath.
The surface activating process effect analysis: by adopting electroless copper novel process and pre-treating technology, coating functions conductive copper layer on target pole material successfully, and bonding force is good; By adopting wicking, chemical tin plating process, activated extremely surface of target, prove that through soldering surface-activation effect is better, inside and outside inner room solder full condition ideal, it is qualified that X ray detects.
The above brazing process technological effect obviously is better than the hit soldering processes of the utmost point of prior art.
Three, utilize above-mentioned target pole material to carry out the coating coating for example:
The employed coating target utmost point as mentioned above, its be the volatilization cathode material, described target pole material is made up of overcoat (1), interior cover (2), interior cover (2) is installed in overcoat (1) inside, is fixedly connected between the two; Wherein: target utmost point lagging material is the Al-Si-Y alloy of casting; The interior cover (2) of the target utmost point is a watercooling jacket, and its material can be selected LY11 for use; Preferably adopt soldering processes fixedly connected as mentioned above between overcoat of the target utmost point (1) and the interior cover (2).
Described target is used to apply the workpiece under the conditions such as high temperature and corrodibility, improving high-temperature oxidation resistant, the corrosion resistance on surface, thereby improves the use properties of workpiece.
Because adopting, described coating contains the aluminium alloy cathode targets of silicon, the heat-resisting element of yttrium as coated material, use coating process of the prior art, be coated with plating coating at piece surface, form Al-Si-Y diffusion alloying high-temperature protection coating, the protection under the environment such as high temperature at workpiece surface.
The metallographic of coating detects: to apply the workpiece of relating operation through coating, at prescribed position, cut metallographic specimen with line, observe under metaloscope.To check that coat-thickness and coating are continuous, whether diffuse interface is qualified.After (referring to Figure 10, Figure 11) checks as can be known quality reach the expection requirement.
Coated component is analyzed:
1) behind the coating coating, its chemical composition analysis the results are shown in following table 4.As can be seen from Table 4, the composition of coating meets the composition range requirement of target behind the coating.
Table 4
| Element | Si | Y | Al |
| The coated material composition | 4.97 | 1.73 | Surplus |
| The target composition range | 4.5～5.5 | 1.1～1.8 | Surplus |
The Phase Structure Analysis of coating (seeing Figure 12): the X-light facies analysis of coating, from Figure 12 result as can be known, the phase structure of described coating is the NiAl phase, is the standard phase structure of resistance to high temperature oxidation.
The high-temperature oxidation resistant of coating, corrosion resistance test:
1) 1100 ℃ of constant temperature oxidation susceptibility tests of coating:
Sample size is 20 * 15 * 3mm, and the constant temperature oxidation test is carried out in still air, and sample is put into the alumina crucible that heating is in advance weighed, and places the muffle furnace that preheats 1100 ℃ to carry out oxidation experiment, and every 20h weighs after taking out and being cooled to room temperature.Analysis Figure 13 is as seen: coating oxidation entered slow build phase in 40 hours.Can draw from Figure 14,15, after 100 hours, coatingsurface generates zone of oxidation all with Al to coating through 1100 ℃ of constant temperature oxidations
2O
3Be main, have minor N iO to exist.Be that coating shows good antioxidant property in 1100 ℃ of constant temperature oxidising processs, the surface has formed complete protective oxide film, and anti-constant temperature oxidation susceptibility is good.
2) 1000 ℃ of cyclic oxidation performance tests of coating: cyclic oxidation test carries out in vertical tube furnace, at 1000 ℃ of insulation 50min, cools off 10min then in air, is a circulation, and totally 100 times, every certain number of times weighing example weight.Can be drawn by Figure 16, in 1000 ℃ of cyclic oxidation processes, coating has good cyclic oxidation performance.
3) coating hot corrosion resistance test:
Crucible method is adopted in the immersed-salt hot corrosion test, sample is immersed fully 850 ℃ 75%Na
2SO
4+ 25%K
2SO
4In the fused salt mixt, take out the back at regular intervals, weighs cook off the salt on surface in boiling water after, observes appearance, renews salt and carry out the next cycle test.Referring to Figure 17.
Figure 18,19 is that coating is at 850 ℃ of 75%Na
2SO
4+ 25%K
2SO
4Surface and the cross section pattern of middle corrosion after 10 hours; Coatingsurface generates zone of oxidation with Al
2O
3Be main, have minor N iO to exist, surface oxide layer has a spot of peeling off.Figure 20,21 is that coating is at 850 ℃ of 75%Na
2SO
4+ 25%K
2SO
4Surface and the cross section pattern of middle corrosion after 60 hours.Coatingsurface generates zone of oxidation and is still by Al
2O
3Form with minor N iO, but surface oxide layer is more loose, peels off seriously, as seen the part has globular NiS to generate.
Can be drawn by Figure 18～21, coating is at 850 ℃ of 75%Na
2SO
4+ 25%K
2SO
4Middle corrosion is after 10 hours, and surface oxide layer has a spot of peeling off; Corrode after 60 hours, zone of oxidation is more loose, peels off seriously, all has been subjected to heavier thermal etching in fused salt.
Conclusion: coated component, thickness, phase structure and high-temperature oxidation resistant, corrosion resistance reach design requirements, obviously are better than prior art, have obtained obviously better technique effect.
Description of drawings:
Fig. 1 is the target pole material structural representation;
Fig. 2 is casting metal die structural representation;
Fig. 3 is the Al-Y alloy phase diagram;
Fig. 4 is YL α X ray picture * 1000;
Fig. 5 is secondary electron image * 1000;
Fig. 6 is Si K α X ray picture * 1000;
Fig. 7 is the Y-Si phasor;
Fig. 8 is electroless copper, zinc-plated structure iron;
Fig. 9 is an overcoat solderer assembling structure synoptic diagram in the target pole material;
Figure 10 be coating metallographic structure 1 *;
Figure 11 be coating metallographic structure 2 500 *;
Figure 12 is the X-light facies analysis of coating;
Figure 13 is that coating is at 1100 ℃ of airborne constant temperature oxidation kinetics curves;
Figure 14 is the surface topographies of 1100 ℃ of constant temperature oxidations of coating after 100 hours;
Figure 15 is the cross section patterns of 1100 ℃ of constant temperature oxidations of coating after 100 hours;
Figure 16 is 1000 ℃ of cyclic oxidation kinetic curves of coating;
Figure 17 is a coating at 850 ℃ corrosion kinetics curve;
Figure 18 is 10 hours a surface topography of coating thermal etching;
Figure 19 is 10 hours a cross section pattern of coating thermal etching;
Figure 20 is 60 hours a surface topography of coating thermal etching;
Figure 21 is 60 hours a cross section pattern of coating thermal etching.
Embodiment:
Related description: among Fig. 8: metallic matrix (701), copper plate (702), tin coating (703); Among Figure 17: corrosive medium: 75%Na
2SO
4+ 25%K
2SO
4).
Embodiment 1
Target pole for coating of the present invention, the correlation technique division is as follows:
One, the target utmost point is formed:
Described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, is fixedly connected between the two.Wherein: overcoat (1) is selected the Al sill for use, and according to weight percent, other composition quality degree except that Al is: Si:4.5～5.5%; Y:1.1～1.8%.Interior cover (2) is a watercooling jacket, requires the material densification, and thermal conductivity is good; Gap between described overcoat (1) and the interior cover (2) is 0.3～2mm, and described overcoat (1) and interior cover (2) form of fixedlying connected between the two is preferably soldering.Described gap is filled up with scolder behind brazing operation, thus the thickness of brazing layer (3) promptly corresponding above gap width.Soldering selects for use scolder to be preferably the Pb sill.The scantlings of the structure of the described target utmost point is preferably as follows: overcoat thickness is 5～40mm; Interior cover thickness is 1～20mm;
Two, target utmost point manufacturing process
One) overcoat manufacturing process
The overcoat of target pole for coating (1) can be cast member.Target utmost point lagging material is the Al-Si-Y alloy of casting.The outer Y of the applying mechanically master alloy of smelting the negative electrode target can adopt vacuum induction melting; External sleeve blank can adopt the method manufacturing of permanent mold casting, bottom pouring type pouring.
The casting technique of the overcoat of target pole material (1):
The overcoat of described target pole for coating material (1) can select for use following starting material to make: commercial-purity aluminium, industrial silicon, Al-Y master alloy.The castingprocesses of described overcoat (1) is: at first melting starting material, casting in metal die (4) then.
Metal die (4) mainly is made up of metal inner core (401), metal die overcoat (402) and metal bed die (403); Wherein metal inner core (401) and metal die overcoat (402) all cooperate installation with metal bed die (403), and metal inner core (401) is installed in metal die overcoat (402) inside.That matches with metal die (2) can also have sand mold loam cake (5) and sprue cup (6).
The casting technique of described target pole for coating overcoat (1) is divided into raw material melting and cast two big steps: described melting technology is: select for use electrical crucible as melting equipment, at first with the crucible preheating, put into the melting raw material then and carry out melting;
The starting material melting technology is: select electrical crucible for use; Prepare burden by the numerical range suitable with each component content of finished product target; Can at first electrical crucible be preheating to 200～400 ℃ during melting, add commercial-purity aluminium and Al-Y master alloy then, it is clear to be warming up to wholeization of furnace charge, and solution temperature to 550 in the adjustment stove～800 ℃, add industrial silicon then, close bell to industrial silicon and melt fully, and can add insulating covering agent; Refining then, and can stir and make the alloy homogenizing; (removing insulating covering agent) also adds the degasifier degasification, removes alloy liquid surface slag afterwards.
Pouring technology is: at first with metal die (4) preheating, and assembling die and cast as requested then.Described preferred pouring technology is: can at first metal die (4) be preheating to 250～550 ℃ and the insulation until metal die (4) everywhere temperature evenly pour into a mould again;
Casting process can be: open bell, remove surface scale; Contain out alloy liquid, treat to pour into a mould when the alloy liquid temp is 650～800 ℃ in the casting ladle, metal die when pouring into a mould simultaneously (4) temperature should be controlled between 200～350 ℃; After treating that casting pressing port solidifies, opening metal mould (4) takes out overcoat (1).
Two) the interior cover (2) of the target utmost point: interior cover is a watercooling jacket, requires the material densification, and thermal conductivity is good.It can select for use modes such as casting to make as the case may be.
Three) described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, and the fixedly connected mode preferred version between the two is to adopt the soldering processes fixed.Gap between the interior overcoat is filled up by brazing layer (3), described gap width just corresponding the thickness of brazing layer (3).Wherein: described overcoat (1) and interior cover (2) between the two soldering select for use scolder to be preferably the Pb sill.
The soldering raw material can be selected technical pure lead, industrial pure tin and industrial star antimony for use; Melting unit is temperature automatically controlled resistance furnace, plumbago crucible and baking oven;
The two process of carrying out soldering of described overcoat (1) and interior cover (2) is: (we select earlier in the copper facing of Al matrix surface, then at the recombining process of copper electroplating surfaces with tin preferably at first overcoat (1) and interior cover (2) to be carried out surface activation process.) with reduce between scolder and the overcoat (1) and scolder and interior cover (2) between angle of wetting, then they are installed on the solderer and load onto the enforcement brazing operation.
Described brazing process is: will be in advance through the sealing that is installed of the overcoat (1) of the target utmost point of surface activation process and interior cover (2), put it into then in the baking oven, under 230～350 ℃ of conditions, be incubated at least 0.5 hour; Melting solder melts technical pure lead under 350～450 ℃ of conditions then, adds industrial pure tin, industrial star antimony then successively, stirs after the fusing fully, and is incubated under 270～390 ℃ of conditions; Target utmost point assembly and scolder that said process was handled carry out soldering cast, 230～350 ℃ of preheating temperatures, 270～390 ℃ of pouring temperatures simultaneously; Behind the casting complete, cooling sheds jig.
Can adopt special tooling (8) to be used for the overcoat (1) of the target utmost point and interior cover (2) are installed and seal, the structure of described special tooling (3) mainly is to have following components to constitute: firm banking (801), holding bolt (802), sprue cup (803).
In the target pole for coating material soldering skill, the overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and the copper plating treatment process that interior cover (2) surface portion carries out surface active according to time sequence are: degreasing, soak heavy ion, strip, electroless copper, wherein:
The degreasing prescription constitutes: OP emulsifying agent, Na
2CO
3, NaPO
3According to mass percent, Na wherein
2CO
3Be 10～30%, NaPO
3: 5～25%; The degreasing process standard is: temperature: 40～80 ℃, and the time: 5～60min;
Soaking heavy ion prescription formation is: composite additive, Ni
2+, CO
2+Wherein: Ni
2+, CO
2+: 30～70g/L; Soaking the heavy ion technological specification is: temperature: 15～30 ℃, and the time: 1～10min;
The decoating liquid prescription is: chromic acid: 4～18g/L, HCL:2～12g/L; The withdrawal plating standard is: temperature: 15～30 ℃, and time 1～2min.
The prescription of electroless copper is: CuSO
45H
2O:60～90g/L; EDTA:80～150g/L; NaH
2PO
2H
2O:20～80g/L; Cl, β γ: 30～60g/L; Ni
2+, Co
2+: 0.1～10g/L; 2-MBT:0.1～10g/L; 1,1-dipyridyl: 1～20mg/L; The chemical-copper-plating process standard is: pH:9～12; Temperature: 60～70 ℃; Plating speed: 8～10 μ m/h; Time: 60～100min.
Adopt the test of thermal shock method, be about to target pole material and be heated to about 600 ℃, insulation 1～1.5h takes out the back shrend, and copper coating does not peel off, and this explanation is good by the copper coating bonding force that this technology obtained.
In the surface activating process process, this process using reductive agent forensic chemistry is zinc-plated, and detailed process is: select following prescription: SnCl for use
2: 3～15g/L, Trisodium Citrate: 50～150g/L, EDTA disodium: 5～30g/L, NaCH
3COO:5～20g/L, TiCl
35～25ml/L, Phenylsulfonic acid: 0.2～5ml/L; Processing parameter is as follows: pH:8.0～10.0, and, temperature: 70～130 ℃.
Target pole for coating of the present invention, the correlation technique division is as follows:
One, the target utmost point is formed:
Described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, is fixedly connected between the two.Wherein: overcoat (1) is selected the Al sill for use, and according to weight percent, other composition quality degree except that Al is: Si:4.5～5.5%:Y:1.1～1.8%; Other composition has preferred requirement in the lagging material, for example Fe≤0.25%.Interior cover (2) is a watercooling jacket, requires the material densification, and thermal conductivity is good; Preferably use the Al sill, according to weight percent, other component content except that Al is: Cu:3.8～4.9%; Mn:0.3～0.9%; Mg:1.2～1.8%; Si≤0.5%; Fe≤0.5%; Zn≤0.3%; Ni≤0.1%; Gap between described overcoat (1) and the interior cover (2) is preferably 0.8～1mm, and described gap is filled up with scolder behind brazing operation, thus the thickness of brazing layer (3) promptly corresponding above gap width.
Described overcoat (1) and interior cover (2) form of fixedlying connected between the two is preferably soldering.Soldering selects for use scolder to be preferably the Pb sill, and according to weight percent, preference can be: other component content except that Pb is: Sn:38～42%; Sb:1.3～2.3%; Impurity≤0.5%.
The scantlings of the structure of described target pole material finished product is preferably as follows: overcoat thickness is preferably 10～30mm; Interior cover thickness is preferably 2～8mm.
Two, target utmost point manufacturing process
One) overcoat manufacturing process
The overcoat of target pole for coating (1) can be cast member: target utmost point lagging material is the Al-Si-Y alloy of casting.The outer Y of the applying mechanically master alloy of smelting the negative electrode target can adopt vacuum induction melting; External sleeve blank can adopt the method manufacturing of permanent mold casting, bottom pouring type pouring.
The casting technique of the overcoat of target pole material (1): the overcoat of described target pole for coating material (1) can select for use following starting material to make: commercial-purity aluminium, industrial silicon, Al-Y master alloy; It preferably can be following scheme that described raw material is formed according to weight percent: the content composition of industrial silicon is: Si is about 99%, and Fe is about 0.3%, and Al is about 0.3%, and Ca is about 0.05%; The content composition of Al-Y master alloy is: Y is about 10%, Fe≤0.15%, other impurity summation≤0.5%.
The castingprocesses of overcoat (1) is: at first melting starting material, casting in metal die (4) then.
Metal die (4) mainly is made up of metal inner core (401), metal die overcoat (402) and metal bed die (403); Wherein metal inner core (401) and metal die overcoat (402) all cooperate installation with metal bed die (403), and metal inner core (401) is installed in metal die overcoat (402) inside.That matches with metal die (2) can also have sand mold loam cake (5) and sprue cup (6).
Before building, go up graphite spraying coating at the metal inner core (401) of metal die (4) earlier, go up the spraying zinc oxide coating at metal die overcoat (402), above-mentioned coating layer required thickness is even, and total coating thickness is no more than 0.4mm; The coating of clearing up metal die (4) surface dirt then and adhering to makes up metal die (4) then, prepares cast; The cast instrument of all uses should spray zinc oxide coating, and is heated to (preferred 350～600 ℃) more than 350 ℃, reduces to room temperature then and uses;
The casting technique of described target pole for coating overcoat (1) is divided into raw material melting and cast two big steps:
Preferred starting material melting technology is in the casting technique of target pole for coating overcoat (1): select plumbago crucible for use; Should clear up crucible before using, guarantee in the crucible and no any other material in surface; Further preferably by following requirement batching: Y prepares burden by about 1.8%, uses Al-Y alloy (Y10%) batching, and (estimate that alloy scaling loss amount is: Si is about 0.5% to Si by about 5% batching; Y is about 1.0%); During melting at first just plumbago crucible be preheating to 250～350 ℃, add commercial-purity aluminium and Al-Y master alloy then, be warming up to wholeization of furnace charge clearly, and solution temperature to 650 in the adjustment stove～750 ℃, add industrial silicon then, close bell to industrial silicon and melt fully; Alloy liquid surface slag is removed in refining under the condition that guarantees alloy liquid homogenizing then; Add the hexachloroethane degasification, add-on is 0.1%～2% of an alloy total amount.Metal die during cast (4) temperature should be controlled between 200～350 ℃; After treating that casting pressing port solidifies, opening metal mould (4) takes out overcoat (1).
Preferred casting process is: earlier metal die (4) is heated to 380～420 ℃ in stove, and is incubated more than 0.5 hour; At first remove surface scale after opening bell, contain out alloy liquid with the exsiccant casting ladle then, carry out thermometric, cast when the alloy liquid temp is 700～750 ℃ in waiting to wrap, metal die when pouring into a mould simultaneously (4) temperature should be controlled between 230～320 ℃; After treating that casting pressing port solidifies, opening metal mould (4) takes out overcoat (1).
Two) manufacture craft of the interior cover (2) of the target utmost point:
Interior cover is watercooling jacket, requires the material densification, and thermal conductivity is good, and its chemical ingredients is the LY12 alloy, therefore selects for use the LY12 hard aluminium alloy bar material can satisfy service requirements fully through mechanical workout.Interior cover adopts LY12 aluminium alloy manufacturing (can be casting), and chemical ingredients should meet the requirement of GB3191-82.
Particularly, interior cover (2) is preferably used the Al sill, and according to weight percent, other component content except that Al preferably can be Cu:3.8～4.9%; Mn:0.3～0.9%; Mg:1.2～1.8%; Si≤0.5%; Fe≤0.5%; Zn≤0.3%; Ni≤0.1%;
Three) described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, and the fixedly connected mode preferred version between the two is to adopt the soldering processes fixed.Gap between the interior overcoat (filled up by brazing layer (3), described gap width just corresponding the thickness of brazing layer (3)) be preferably 0.8～1mm.Wherein: described overcoat (1) and interior cover (2) between the two soldering select for use scolder to be preferably the Pb sill, it is as follows preferably to form proportioning: according to weight percent, the quality percentage composition of other composition except that Pb is: Sn:38～42%; Sb:1.3～2.3%; Impurity≤0.5%.
The chemical ingredients (%) of the preferred braze of table 1
| Element | Sn | Sb | Pb | Cu | As | S | Fe | Zn | Ni | Al |
| Content | 39 - 41 | 1.5 - 2.0 | Matrix | ≤ 0.0 8 | ≤ 0.0 5 | ≤ 0.0 2 | ≤ 0.0 5 | ≤ 0.00 2 | ≤ 0.1 | ≤ 0.00 5 |
A kind of target pole material soldering process for coating layer, soldering raw material are selected technical pure lead, industrial pure tin and industrial star antimony for use; Melting unit is temperature automatically controlled resistance furnace, plumbago crucible and baking oven;
The two process of carrying out soldering of described overcoat (1) and interior cover (2) is: at first to overcoat (1) and interior cover (2) carry out surface activation process with reduce between scolder and the overcoat (1) and scolder and interior cover (2) between angle of wetting, then they are installed on the solderer and load onto the enforcement brazing operation.
The research of the surface activating process of target pole material:
Select earlier in the copper facing of Al matrix surface, then at the recombining process of copper electroplating surfaces with tin.Using this technology to plate one deck preferred thickness uniformly at the internal surface of the outside surface of interior cover (2) and overcoat (1) is about the copper coating of 5-8 μ m and plates one deck preferred thickness on the copper coating surface and be about 10-15 μ m, compact tin coating.
Before soldering preferably be: the overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and interior cover (2) surface portion carries out copper plating treatment and carry out zinc-plated processing again on the copper surface to the overcoat (1) of the target utmost point and the surface activation process of interior cover (2).
Chemical-copper-plating process: (for example: inferior sodium phosphate) make the cupric ion of the free state in the copper electrolyte be reduced into solid-state copper crystal and be coated in workpiece surface by the reductive agent that is fit to.
The overcoat (1) of the target utmost point that brazing solder can touch when implementing soldering and the preferred process that interior cover (2) surface portion carries out copper plating treatment are successively: degreasing, wash, soak heavy ion, strip, washing, electroless copper, washing, drying; Water washing process is for adopting the washing of deionized water room temperature, and the time is preferably 1～5min; Wherein:
The degreasing prescription constitutes: OP emulsifying agent, Na
2CO
3, NaPO
3According to mass percent, Na wherein
2CO
3Be 10～30%, NaPO
3: 5～25%; The degreasing process standard is; Temperature: 40～80 ℃, the time: 5～60min; Soaking heavy ion prescription formation is: composite additive, Ni
2+, CO
2+Wherein: Ni
2+, CO
2+: 30～70g/L; Soaking the heavy ion technological specification is: temperature: 15～30 ℃, and the time: 1～10min; The decoating liquid prescription is: chromic acid: 4～18g/L, HCL:2～12g/L; The withdrawal plating standard is: temperature: 15～30 ℃, and time 1～2min.
The chemical bronze plating liquid main component of novel process has: mantoquita, complexing agent, reductive agent, pH value are adjusted agent, are separated out promotor, trace mineral supplement, solution stabilizer etc.The prescription of electroless copper is: CuSO
45H
2O:60～90g/L; EDTA:80～150g/L; NaH
2PO
2H
2O:20～80g/L; C1, β γ: 30～60g/L; Ni
2+, Co
2+: 0.1～10g/L; 2-MBT:0.1～10g/L; 1,1-dipyridyl: 1～20mg/L; The chemical-copper-plating process standard is: pH:9～12; Temperature: 60～70 ℃; Plating speed: 8～10 μ m/h; Time: 60～100min.
Adopt the test of thermal shock method, target pole material is heated to about 600 ℃, insulation 1～1.5h takes out the back shrend, and copper coating does not peel off, and this explanation is good by the copper coating bonding force that this technology obtained.
Tin plating technique research: after the surfaces externally and internally of target pole material applies one deck conductive copper, the excellent wetting capacity energy is arranged, in the substrate of copper coating, hang up one deck tin again in order to make coating and braze (pewter, 280 ℃ of fusing points).
Chemical plating stannum on the wicking layer adopts the reductive agent forensic chemistry zinc-plated, and detailed process is: select following prescription: SnC1 for use
2: 3～15g/L, Trisodium Citrate: 50～150g/L, EDTA disodium: 5～30g/L, NaCH
3COO:5～20g/L, TiCl
3: 5～25ml/L, Phenylsulfonic acid: 0.2～5ml/L; Processing parameter is as follows: pH:8.0～10.0, and, temperature; 70～130 ℃.Wherein: Trisodium Citrate is Sn in the plating bath
2+Complexing agent, further preferred concentration is 80～120g/L, is the best with about 100g/L.EDTA two na concns with about 10～20g/L for better.
Described prescription and the technological specification that on copper coating, carries out chemical wicking: Sn
2+: 10～20g/L; HCl:10～20g/L; N
2H
4CS:35～50g/L; Temperature: 50～80 ℃; Time: 1～2min.
Target pole material soldering process for coating layer, it is characterized in that: described brazing process is preferably: will be in advance through the sealing that is installed of the overcoat (1) of the target utmost point of surface activation process and interior cover (2), put it into then in the baking oven, insulation is at least 1～4 hours under 280～300 ℃ of conditions;
Melting solder melts Pb under 350～450 ℃ of conditions then, adds Sn, Sb successively, stirs after the fusing fully, and is incubated under 270～390 ℃ of conditions; Target utmost point assembly (overcoat (1) and the interior cover (2) that comprise the target utmost point) and scolder that said process was handled carry out soldering cast, 280～300 ℃ of preheating temperatures, 320～340 ℃ of pouring temperatures simultaneously.Behind the casting complete, cooling sheds jig.
Can adopt special tooling (8) to be used for the overcoat (1) of the target utmost point and interior cover (2) are installed and seal in the target pole material soldering skill, the structure of described special tooling (3) mainly is that the following components formation is arranged: firm banking (801), holding bolt (802), sprue cup (803); For ease of the location of the installation before the soldering, can also select gap pin (804) for use.
Claims (4)
1. the casting technique of the overcoat of a target pole for coating, described target extremely mainly is made up of overcoat (1), interior cover (2), and interior cover (2) is installed in overcoat (1) inside, is fixedly connected between the two; Wherein: overcoat (1) is selected the Al sill for use, and according to weight percent, other composition quality percentage composition except that Al is: Si:4.5～5.5%; Y:1.1～1.8%;
The manufacture method of described overcoat (1) is casting; The overcoat of described target pole for coating selects for use following starting material to make: commercial-purity aluminium, industrial silicon, Al-Y master alloy;
The castingprocesses of described overcoat (1) is: at first melting starting material, casting in metal die (4) then;
It is characterized in that:
Described raw material is according to mass percent, and the content composition of industrial silicon is: Si 99%, and Fe 0.3%, and Al 0.3%, and Ca 0.05%; The content composition of Al-Y master alloy is: Y 10%, Fe≤0.15%, other impurity summation≤0.5%; The raw-material technological process of described melting is:
Select electrical crucible for use; It is preheating to 200～400 ℃, adds commercial-purity aluminium and Al-Y master alloy then, be warming up to wholeization of furnace charge clearly, and solution temperature to 550 in the adjustment stove～800 ℃, add industrial silicon then, close bell to industrial silicon and melt fully; Alloy liquid surface slag is removed in refining then, and degasification.
2. according to the casting technique of the overcoat of the described target pole for coating of claim 1, it is characterized in that: the raw-material technological process of described melting is:
Described electrical crucible is a plumbago crucible; Plumbago crucible is preheating to 250～350 ℃, adds commercial-purity aluminium and Al-Y master alloy then, be warming up to wholeization of furnace charge clearly, and solution temperature to 650 in the adjustment stove～750 ℃, add industrial silicon then, close bell to industrial silicon and melt fully; Alloy liquid surface slag is removed in refining under the condition that guarantees alloy liquid homogenizing then; Add the hexachloroethane degasification, add-on is 0.1%～1% of an alloy liquid total amount.
3. according to the casting technique of the overcoat of the described target pole for coating of claim 2, it is characterized in that: pouring technology is:
At first metal die (4) is preheating to 250～550 ℃ and the insulation temperature is even everywhere until mould;
Casting process is: open bell, remove surface scale; Contain out alloy liquid, the alloy liquid temp is 650～800 ℃ of cast in the casting ladle, and metal die (4) temperature is controlled between 200～350 ℃ in the casting process simultaneously;
After treating that rising head solidifies, opening metal mould (4) takes out overcoat (1).
4. according to the casting technique of the overcoat of the described target pole for coating of claim 3, it is characterized in that: described pouring technology is:
Metal inner core (401) at metal die (4) is gone up graphite spraying coating earlier before cast, goes up the spraying zinc oxide coating at metal die overcoat (402), and above-mentioned coating layer required thickness is even, and total coating thickness is no more than 0.4mm;
The coating of clearing up metal die (4) surface dirt then and adhering to, recombinant metal die (4) is prepared cast; The cast instrument spraying zinc oxide coating of all uses, and be heated to more than 350 ℃, reduce to room temperature then and use;
At first metal die is heated to 380～420 ℃ in stove, and is incubated more than 0.5 hour;
Concrete casting process is:
At first remove surface scale after opening bell, contain out alloy liquid with the exsiccant casting ladle then, carry out thermometric, the alloy liquid temp is 700～750 ℃ of cast in the bag, and casting metal mould (4) temperature is controlled between 230～320 ℃ simultaneously;
After treating that rising head solidifies, opening metal mould (4) takes out overcoat (1).
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| CNB2005100469015A CN100464004C (en) | 2005-07-21 | 2005-07-21 | Target pole for coating and its casting process for external sleeve |
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| CNB2005100469015A CN100464004C (en) | 2005-07-21 | 2005-07-21 | Target pole for coating and its casting process for external sleeve |
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| CN100464004C true CN100464004C (en) | 2009-02-25 |
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| CN102430718A (en) * | 2011-12-26 | 2012-05-02 | 昆山全亚冠环保科技有限公司 | Mould for preparing aluminum and aluminum alloy rotary target and manufacturing method thereof |
| CN115094392A (en) * | 2022-07-06 | 2022-09-23 | 天津华瑞新材料科技有限公司 | Preparation method of fine-grain high-density nickel-chromium-aluminum-yttrium-silicon alloy target material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204284A (en) * | 2002-12-25 | 2004-07-22 | Toshiba Corp | Sputtering target, al alloy film, and electronic component |
| CN1607265A (en) * | 2003-10-13 | 2005-04-20 | 沈阳黎明航空发动机(集团)有限责任公司 | Process for preparation of high-temperature protecting coating by vacuum arc deposition |
| CN1607264A (en) * | 2003-10-13 | 2005-04-20 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for preparing aluminum-silicon-yttrium diffusion alloying coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004204284A (en) * | 2002-12-25 | 2004-07-22 | Toshiba Corp | Sputtering target, al alloy film, and electronic component |
| CN1607265A (en) * | 2003-10-13 | 2005-04-20 | 沈阳黎明航空发动机(集团)有限责任公司 | Process for preparation of high-temperature protecting coating by vacuum arc deposition |
| CN1607264A (en) * | 2003-10-13 | 2005-04-20 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for preparing aluminum-silicon-yttrium diffusion alloying coating |
Non-Patent Citations (2)
| Title |
|---|
| 阴极靶材外套的研究与制备. 曲彦平，杨胜群，史凤岭，魏明霞，董满中.铸造，第54卷第6期. 2005 |
| 阴极靶材外套的研究与制备. 曲彦平，杨胜群，史凤岭，魏明霞，董满中.铸造，第54卷第6期. 2005 * |
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