CN103255413B - Copper and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use and preparation technology - Google Patents
Copper and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use and preparation technology Download PDFInfo
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Abstract
The invention discloses a kind of copper and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use and preparation technology thereof, comprise the following steps: copper and copper alloy surface are carried out to activation processing; According to the cobalt-base alloys of 60-70vol.%, the titanium carbide of 10-30vol.%, the proportioning preparation raw material of the calcirm-fluoride of 10-30vol.%, evenly mixes; Above-mentioned composite coating precursor raw material is mixed with binding agent, be preset at copper or copper alloy surface, form binding agent fore-put powder layer, under inert gas shielding, adopt Pulse Nd: YAG laser instrument carries out bonding agent fore-put powder layer described in laser irradiation; Or powder feeder synchronous powder feeding system is sent into the powder preparing under laser beam; Powder smelting solidifies rear formation cobalt-based self-lubricating composite coating. The self-lubricating coat in use that the present invention prepares has the good lubricated effect of anti-friction scrape along antifriction, can meet the instructions for use of copper under harsh working condition and alloy part thereof.
Description
Technical field
The invention belongs to materials science field, relate in particular to a kind of copper and copper alloy surface Metal SubstrateThe preparation method of self-lubricating coat in use.
Background technology
Copper and copper alloy is day by day wide because having excellent electric conductivity, high thermal conductivity and good plasticityBe applied to the fields such as electric power, metallurgy, mechanized equipment, Aero-Space generally. But, copper and copper alloyAs the workpiece under harsh working condition as continuous cast mold, blast-furnace tuyere etc. require low deflection,High abrasion, low-friction coefficient etc., it is difficult to direct engineering demands. Especially copper and copper alloy materialFriction system when material is joined pair or the secondary slip of autogamy with other material (as metal) under unlubricated ambient conditionNumber is very high, and causes serious adhesive wear, and the engineering application of copper and copper alloy friction component is subject toConsiderable restraint. Copper and Cu alloy material process for modifying surface both can keep good the leading of copper matrix itselfHeat, electric conductivity, can strengthen its case hardness, wearability, anti-corrosion by process for modifying surface againProperty and antiwear and friction reduction property thereof etc. Laser melting coating, as a kind of advanced person's process for modifying surface, utilizes highThe feature that energy laser beam focus energy is high, moment is by preset at substrate surface or with laser synchronizationPowder melts completely, and base material part fusing simultaneously, forms a kind of new composite, laser beam flyingRear rapid solidification, obtains and the fine and close coat of matrix metallurgical binding, reaches the object of surface modification.
Form following patent around copper and copper alloy surface laser melting and coating technique and material at present:
1, for laser cladding of material and the cladding method of aluminium bronze. China Patent Publication No.101255522 disclose a kind of method for aluminium bronze surface laser cladding, but its cladding material is mainFor surface peening and the reparation of aluminium bronze, do not possess the function such as antiwear and antifriction or self-lubricating property, because ofThis cannot be competent in the Service Environment that requires low fretting wear under unlubricated ambient condition.
2, copper and copper alloy surface laser melting coating composite wear-resistant layer and preparation method. China Patent Publication No.102041503A discloses a kind of copper and copper alloy surface laser melting coating composite wear-resistant layer and preparation method,Its composite wear-resistant layer is at least made up of two-layer or two-layer above multilayer cobalt-base alloys cladding layer, passes throughThe transition of Ni-Al transition zone, the bond strength of raising cobalt-based coating and copper alloy. Although this coating can shapeBecome the cladding layer of about 2mm, and coating densification, flawless, pore, but high temperature (400 DEG C withOn), lubricant grease lost efficacy or unlubricated ambient condition under, it is high wear-resisting that it cannot ensure that coating hasProperty and low coefficient of friction.
Although the technique scheme that prior art provides can utilize laser melting and coating process to copper and copper alloyWear-resistant coating processing is carried out on surface, and by matching suitable cladding material or taking the method for transition zoneOvercome the non-uniformity problem of cladding layer crackle, pore and microstructure, obtained certain technology effectReally. But for lubricant grease lost efficacy or unlubricated ambient condition under, cannot ensure that coating has high resistance toMill property and low coefficient of friction.
Retrieve verification through applicant: adopt laser melting and coating process to prepare Metal Substrate at copper and copper alloy surfaceSelf-lubricating coat in use, the domestic precedent that there is no, does not see relevant report abroad yet. Therefore, find suitablySelf-lubricating composite system, complete copper and copper alloy surface self-lubricating by laser melting and coating process and be coated withThe preparation method of layer, still needs those skilled in the art further to make creationary research work.
Summary of the invention
The object of the invention is to lose efficacy or unlubricated ambient condition at lubricant grease for copper and copper alloyA lower difficult problem for antiwear and antifriction and the problem that prior art exists of realizing, proposes a kind of copper and copper alloy surfaceLaser melting coating cobalt-based self-lubricating coat in use, makes itself and copper realize metallurgical binding, and at high temperature has from profitSlide function, propose a kind of preparation technology of above-mentioned coating simultaneously, can accurately control coating layer thickness,Have energy consumption low, pollution-free, efficiency is high, the feature that cost is low.
For achieving the above object, the present invention adopts following technical scheme:
A preparation technology for copper and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use, its feature existsIn: comprise the following steps:
(1) copper and copper alloy surface are carried out to activation processing;
(2) preparation composite coating precursor material: according to the cobalt-base alloys of 60-70vol.%, 10-30The titanium carbide of vol.%, the proportioning of the calcirm-fluoride of 10-30vol.% measures raw material, evenly mixes; Wherein,Cobalt-base alloys granularity is 45～100 μ m, titanium carbide 10-20 μ m, calcirm-fluoride 1-3 μ m;
(3) above-mentioned composite coating precursor raw material is mixed with binding agent, be preset at through step (1)Copper or the copper alloy surface processed, form binding agent fore-put powder layer, and preset thickness is 0.7-1.2mm,Under inert gas shielding, adopt Pulse Nd: it is preset that YAG laser instrument carries out described in laser irradiation bonding agentPowder bed; Or powder feeder synchronous powder feeding system is sent into the powder preparing under laser beam; After powder smelting solidifiesForm cobalt-based self-lubricating composite coating.
Described Pulse Nd: the mean power of YAG laser instrument is 350-400W, and sweep speed is5-10mm/s, spot diameter 1-1.5mm.
Composite coating precursor raw material is 3:1 with binding agent mixed volume ratio.
The copper that above-mentioned technique is prepared and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use thickness are0.5-1mm。
Compared with prior art, the present invention utilizes the little and low 400WNd:YAG solid of price of volumeLaser instrument, on copper and copper alloy substrate or part with the wear-resistant cobalt-base alloys of high temperature, hard titanium carbideAs presoma constituent element, by allocating each constituent element volume fraction, laser is molten with solid lubrication body calcirm-fluorideCover the self-lubricating composite coating that preparation is resistance to worn and had low-friction coefficient. The compound painting of this cobalt-based self-lubricatingLayer tissue densification, flawless, pore, form good metallurgical binding with copper and copper alloy, can formThe coating of 0.5-1mm. Preparation method of the present invention can accurately control the thickness of self-lubricating coat in useAnd whole process easily is automated control, there is low energy consumption, pollution-free, efficiency is high, and cost is lowAdvantage.
Brief description of the drawings
Fig. 1 is red copper surface laser cladding Co-based alloy/20%TiC/10%CaF2Self-lubricating coat in use entirety shapeLooks.
Fig. 2 is red copper surface laser cladding Co-based alloy/20%TiC/10%CaF2Self-lubricating coat in use is high to be shownMicro-tissue topography.
Fig. 3 is Cr-Zr-Cu copper alloy surface laser cladding Co-based alloy/10%TiC/20%CaF2Self-lubricatingCoating entirety pattern.
Fig. 4 is Cr-Zr-Cu copper alloy surface laser cladding Co-based alloy/10%TiC/20%CaF2Self-lubricatingCoating high power displaing micro tissue topography.
Fig. 5 is Cr-Zr-Cu copper alloy surface laser melting coating cobalt-based self-lubricating coat in use hardness distribution, whereinOrdinate is hardness, and abscissa is the degree of depth apart from coating surface, the mm of unit.
Fig. 6 is Cr-Zr-Cu copper alloy surface laser melting coating cobalt-based self-lubricating coat in use and pure laser melting coating cobalt-basedThe coefficient of sliding friction comparison diagram of alloy coat, wherein ordinate is coefficient of friction, abscissa is for slidingDistance, the m of unit.
Detailed description of the invention
Embodiment 1:
The present embodiment is long at 800() × 500(is wide) × 10(is thick) the copper plate surface of mm adoptsNd:YAG laser instrument carries out laser melting coating cobalt-based self-lubricating composite coating, and its preparation method is according to following stepSuddenly carry out:
1, copper plate surface activation process
Polish roughening treatment or adopt of 60# coarse sandpaper for the copper plate that is 10mm to thickness surfaceWith the processing of sand-blasting machine surface sand-blasting, remove surface oxide layer and spot, to strengthen red copper surface and cobalt-basedThe combination of self-lubricating composite cladding layer, then cleans natural air drying with acetone.
2, preparation cobalt-based is from the lubricated composite precursor of powder bed, preset cladding powder bed
By following compositions (percent by volume) preparation laser melting coating presoma 70vol.%(percent by volume)Cobalt-base alloys, cobalt-base alloys composition is that cobalt-base alloys composition is C:1.0, Cr:17, Ni:17, W:7.0, Si:0.2, Mn:0.3, Fe:1.0, surplus is Co (wt.%); Take 20vol.%(bodyLong-pending percentage) titanium carbide and 10vol.%(percent by volume) calcirm-fluoride. Above-mentioned each raw material grainDegree is: it is 45～100 μ m that cobalt-based closes powder stock granularity, titanium carbide 10-20 μ m, calcirm-fluoride 1-3 μ m.Above-mentioned raw materials mixes, then itself and bonding agent (cellulose acetate organic solvent) are mixed into pasty stateOr paste, mixed proportion is 3:1(volume ratio), after mixing and stirring, be evenly coated in surface and liveChange on copper plate after treatment surface, carry out compacting and surface physics smooth, coating thickness 1-1.2mm,Then natural air drying.
3, laser melting coating is prepared cobalt-based self-lubricating coat in use
The copper plate that presets cobalt-based self-lubricating composite powder is put in to Nd:YAG laser-processing systemOn CNC lathe, carry out Laser Cladding Treatment, laser cladding technological parameter is: laser power 350W,Sweep speed 5mm/s, laser pulse width 0.5ms, spot size 1mm, overlapping rate 30%. Laser is sweptAfter having retouched, red copper surface forms flawless, imperforate large area laser overlapping cladding layer, cladding bed thicknessSpend about 0.9-1mm.
Overall pattern and the microscopic structure shape of the present embodiment red copper surface laser melting coating cobalt-based self-lubricating coat in useLooks as shown in Figure 1 and Figure 2. Through friction-wear test, self-lubricating coat in use coefficient of friction and wear rate along withThe increase of the sliding distance trend that tapers off, has obviously self-lubricating function.
Embodiment 2: the present embodiment is long at 500() × 500(is wide) × 10(is thick) continuous casting of mmCrystallizer material C r-Zr-Cu copper alloy plate surface adopts Nd:YAG laser instrument to carry out laser melting coating cobalt-based certainlyLubricated composite coating, its preparation method carries out according to following steps:
1, copper plate surface activation process
The Cr-Zr-Cu copper alloy surface that is 10mm to thickness adopts the processing of sand-blasting machine surface sand-blasting, removesSurface oxide layer and spot, to strengthen Cr-Zr-Cu copper alloy surface and cobalt-based self-lubricating composite cladding layerIn conjunction with, then clean natural air drying with acetone.
2, preparation cobalt-based is from the lubricated composite precursor of powder bed, preset cladding powder bed
By following compositions (percent by volume) preparation laser melting coating presoma 70vol.%(percent by volume)Cobalt-base alloys, cobalt-base alloys composition is that cobalt-base alloys composition is C:1.3, Cr:21, Ni:18, W:8.0, Si:0.4, Mn:0.2, Fe:0.8, surplus is that Co (wt.%) takes 10vol.%(volumePercentage) titanium carbide and 20vol.%(percent by volume) calcirm-fluoride. Above-mentioned each raw material granularityFor: it is 45～100 μ m that cobalt-based closes powder stock granularity, titanium carbide 10-20 μ m, calcirm-fluoride 1-3 μ m.
3, laser melting coating is prepared cobalt-based self-lubricating coat in use
Above-mentioned raw materials mixes, and adopts Granulation Equipments to carry out granulation, dries. Then adopt roller typeNegative pressure powder feeder is sent into laser molten pool (Cr-Zr-Cu copper alloy by above-mentioned prilling powder with the flow of 10g/sSurface), on the CNC of Nd:YAG laser-processing system lathe, carry out Laser Cladding Treatment, laserMelting and coating process parameter is: laser power 400W, sweep speed 5mm/s, laser pulse width 0.5ms, lightSpot size 1.5mm, overlapping rate 40%. After laser scanning completes, Cr-Zr-Cu copper alloy surface forms nothingCrackle, imperforate large area laser overlapping cladding layer, the about 1mm of cladding layer thickness.
The overall pattern of the present embodiment Cr-Zr-Cu copper alloy surface laser melting coating cobalt-based self-lubricating coat in use andDisplaing micro tissue topography as shown in Figure 3, Figure 4. The self-lubricating of Cr-Zr-Cu copper alloy surface laser melting coating cobalt-basedThe microhardness distribution of coating as shown in Figure 5, about 820HV0.1, pure cobalt-base alloys cladding layer is micro-hardSpend about 480HV0.1, the about 98HV of Cr-Zr-Cu copper alloy microhardness0.1. As shown in Figure 6, through rubbingWipe wear test, self-lubricating coat in use coefficient of friction is obvious reduction trend, and coefficient of friction is along with slipThe increase of distance is down to below 0.2.
The above is preferred embodiment of the present invention, but the present invention should not be confined to this enforcementThe disclosed content of example. Do not depart from the equivalence completing under principles of this disclosure so every or repairChange, all fall into the scope of protection of the invention.
Claims (4)
1. a preparation technology for copper and copper alloy surface laser melting coating cobalt-based self-lubricating coat in use, its feature existsIn comprising the following steps:
(1) copper or copper alloy surface are carried out to activation processing;
(2) preparation composite coating precursor material: according to the cobalt-base alloys of 60-70vol.%, 10-30The titanium carbide of vol.%, the proportioning preparation raw material of the calcirm-fluoride of 10-30vol.%, evenly mixes; Wherein,Cobalt-base alloys granularity is 45～100 μ m, titanium carbide 10-20 μ m, calcirm-fluoride 1-3 μ m;
(3) above-mentioned composite coating precursor material is mixed with binding agent, be preset at through step (1)Copper or the copper alloy surface processed, form binding agent fore-put powder layer, and preset thickness is 0.7-1.2mm,Under inert gas shielding, adopt Pulse Nd: it is pre-that YAG laser instrument carries out described in laser irradiation binding agentPut powder bed; Or powder feeder synchronous powder feeding system is sent into the powder preparing under laser beam; Powder smelting solidifiesRear formation cobalt-based self-lubricating composite coating.
2. copper according to claim 1 and copper alloy surface laser melting coating cobalt-based self-lubricating coat in usePreparation technology, is characterized in that: described Pulse Nd: the mean power of YAG laser instrument is 350-400W,Sweep speed is 5-10mm/s, spot diameter 1-1.5mm.
3. copper according to claim 1 and copper alloy surface laser melting coating cobalt-based self-lubricating coat in usePreparation technology, is characterized in that: composite coating precursor material is 3:1 with binding agent mixed volume ratio.
4. copper and the copper alloy surface laser melting coating prepared according to the technique described in claim 1,2 or 3Cobalt-based self-lubricating composite coating, is characterized in that: described laser melting coating cobalt-based self-lubricating coat in use thickness is0.5-1mm。
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| CN105543841A (en) * | 2016-01-07 | 2016-05-04 | 辽宁思达思克实业有限公司 | Method for preparing composite abrasion-resistant layer on copper-based bearing alloy surface through laser cladding |
| CN106048606B (en) * | 2016-08-12 | 2019-07-12 | 沈阳航空航天大学 | Spheroidal graphite cast-iron surface TiC/ cobalt-base alloys composite coating and its laser melting coating preparation process and application |
| CN106283043A (en) * | 2016-11-10 | 2017-01-04 | 上海工程技术大学 | A kind of laser melting coating cobalt-based self-lubricating coat in use preparation facilities and method |
| CN113621957A (en) * | 2021-07-06 | 2021-11-09 | 燕山大学 | Preparation method of self-lubricating phase composite coating by laser cladding in-situ synthesis |
| CN114481122A (en) * | 2022-01-14 | 2022-05-13 | 中国人民解放军军事科学院国防科技创新研究院 | Additive manufacturing surface coating preparation method and device |
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| CN102041503A (en) * | 2009-12-29 | 2011-05-04 | 华中科技大学 | Laser-cladded composite wear-resisting layer on surfaces of copper and copper alloys and preparation method |
| CN102650012A (en) * | 2012-05-05 | 2012-08-29 | 张家港市和昊激光科技有限公司 | Special cobalt-based metal ceramic alloy powder for optical fiber laser cladding |
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| CN101381869A (en) * | 2008-10-22 | 2009-03-11 | 东莞理工学院 | Alloy powder special for laser-remelted high hardness crackless iron-base alloy |
| CN101748401A (en) * | 2008-12-19 | 2010-06-23 | 中国科学院兰州化学物理研究所 | Method for plating high-temperature self-lubricating coating on metal surface through laser |
| CN102041503A (en) * | 2009-12-29 | 2011-05-04 | 华中科技大学 | Laser-cladded composite wear-resisting layer on surfaces of copper and copper alloys and preparation method |
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