CN107287592B - A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method - Google Patents

A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method Download PDF

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CN107287592B
CN107287592B CN201710689950.3A CN201710689950A CN107287592B CN 107287592 B CN107287592 B CN 107287592B CN 201710689950 A CN201710689950 A CN 201710689950A CN 107287592 B CN107287592 B CN 107287592B
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cladding
powder
fine copper
laser
cladding layer
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CN107287592A (en
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战再吉
吕相哲
曹海要
王振春
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Yanshan University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides

Abstract

The invention discloses a kind of fine copper surface laser claddings to prepare zirconium dioxide-boron carbide enhancing cladding layer method, the described method comprises the following steps: preparation Ceramic Composite enhancing cladding powder；The surface preparation of fine copper matrix to cladding；Make Ceramic Composite enhancing cladding powder in the rapid consolidation in the surface of fine copper matrix using laser cladding apparatus using synchronous powder feeding system mode, form ZrO2‑B4C ceramics enhance cladding layer, and the fine copper matrix after cladding is air-cooled to room temperature.Present invention cladding layer obtained, can be improved the mechanical property of cladding layer, finally obtain the cladding layer that homogeneity of ingredients can be excellent on fine copper surface.

Description

A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer Method
Technical field
The invention belongs to Surface Engineering fields, are related to a kind of fine copper surface laser cladding preparation Ceramic Composite enhancing cladding layer Method, i.e., the fine copper Surface Creation ZrO under laser action2-B4C enhances cladding layer.
Background technique
Fine copper has high thermal conductivity and excellent plasticity and toughness, but its intensity and wear-resisting property are poor, no It is suitble to work under conditions of high load capacity；Ceramic material has high hardness, good wearability and high-temperature stability；By the two In conjunction with preparing copper-based ceramic composite, so that it is had good thermal conductivity and have both high wearability, improve copper material The service life of material expands use scope.
Laser melting and coating technique as a kind of advanced surface increases material manufacturing technology, by high energy laser beam make cladding material with Matrix while melting and solidification, obtain the enhancement layer of metallurgical bonding.
Laser melting and coating technique has the following advantages compared to other sufacings: (1) laser heating is rapid, cooling velocity fast (106 DEG C/s), cools tissue is typical rapid solidification structure.(2) the laser action time is short, and thermal distoftion is small, dilute it is low, and cladding layer with Matrix is metallurgical bonding.(3) laser melting coating range is accurate, flexible operation, and raw material uses few.(4) cladding powder range of choice is wide. (5) control easy to automate.
Laser melting coating process equipment is the system of a set of complexity.Specifically include that (1) laser (CO2Laser, YAG laser Device, semiconductor laser, optical fiber laser) and light path system.It generates laser and conducts to machining area.(2) powder feeding equipment (is sent Powder device, powder delivery channel and nozzle).Cladding powder is conveyed to molten bath.(3) platform is laser machined.Multi-coordinate numerically-controlled machine tool or Puma manipulator realizes the relative motion between laser beam and workpiece according to setting path.(4) ancillary equipment.Control climate system System, detection and feedback control system and cooling system.Copper is different to the laser absorption rate of different wave length, semiconductor light fibre laser The optical maser wavelength emitted is 1.064 μm, CO2The optical maser wavelength that laser is emitted is 10.6 μm, and copper is right under the same conditions The former absorptivity is about 7 times of the latter, therefore is conducive to the laser melting coating on copper surface using semiconductor light fibre laser.
Therefore it can use the ceramics enhancing cladding layer that laser melting and coating technique has good comprehensive performance in the preparation of copper surface. Two kinds of reinforcing materials are provided commonly for laser melting coating, and there are no relevant researchs, while the reinforcing effect of polynary ceramics is better than unit Ceramics, therefore study and prepare a kind of laser melting coating and be of great significance with copper-based ceramic reinforced composite.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of fine copper surface preparation Ceramic Composite enhancing cladding layer, utilize Gao Gong Rate laser is in fine copper Surface Creation ZrO2-B4The preparation process of C enhancing cladding layer.
To achieve the goals above, the technical scheme is that
A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method, the method includes Following steps:
A: preparation Ceramic Composite enhances cladding powder；
B: the surface preparation of the fine copper matrix to cladding；
C: using synchronous powder feeding system mode, using laser cladding apparatus, makes Ceramic Composite enhancing cladding powder in fine copper matrix The rapid consolidation in surface, formed ceramics enhancing cladding layer；
D: the fine copper matrix after cladding is air-cooled to room temperature；
The wherein sequence interchangeable of step A and step B.
Further, the Ceramic Composite enhances the amount of each component in cladding powder by weight percentage are as follows: 5~10% ZrO2Powder, 5~20%Ni packet B4C powder, surplus are Cu powder.
Further, the ZrO2Powder and Ni packet B4The mass ratio of C powder is 1:1~2.
Further, the Ceramic Composite, which enhances the specific preparation method of cladding powder, is, by each raw material powder according to institute The full and uniform mixing of percentage is stated, is then placed in drying box, dries 1h at 120 DEG C, obtains Ceramic Composite enhancing cladding powder End.
Further, the full and uniform mixed specific method of the raw material powder is to utilize V-type batch mixer, speed of agitator For 15r/min, incorporation time 2h.
Further, the ZrO2The granularity of powder is 25~48 μm, purity 99.9%；The Ni packet B4The granularity of C is 25 ~48 μm, B4C content is 60wt.%；The granularity of the Cu powder is 53~75 μm, purity 99.9%.
Further, the step B the following steps are included:
B1: the fine copper matrix using sand paper polishing to cladding, to remove surface blot, oxide；
B2: the surface using dehydrated alcohol wiping to the fine copper matrix of cladding；
B3: in one layer of carbon black ink of external coating of fine copper matrix, being put into drying box, the dry 10min at 120 DEG C.
Further, the laser cladding apparatus in step C includes laser, movable fixture and paraxonic powder feeder, The semiconductor light fibre laser that the laser is 1.064 μm, laser power are 1800~2200W, and overlapping rate is 30~50%； The movable fixture is for fixing fine copper matrix, and movement speed is 1~2mm/s；The paraxonic powder feeder is by Ceramic Composite Enhancing cladding powder is sent at LASER SPECKLE, and load powder gas is argon gas, and throughput is 2~6L/min, and powder sending quantity is 1~2g/ min。
Further, the fine copper matrix also needs to carry out the pre-heat treatment before carrying out laser melting coating, makes to the pure of cladding Copper substrate surface temperature reaches 500 DEG C.
Further, the specific method of the pre-heat treatment is, according to the size of fine copper matrix, using 1400~ The low power laser of 1600W irradiates 5~6min to fine copper matrix surface.
The beneficial effects of the present invention are: the present invention is prepared for ceramic enhancing in fine copper matrix surface using laser melting and coating technique Cladding layer.The present invention uses two different ceramic phases, and morphosis is different, composite strengthening significant effect.Cladding of the present invention Layer inner ceramic reinforced phase distribution gradient, reduces thermal stress-cracking.It is convenient that cladding powder used in the present invention is prepared, application Range is wide.
Detailed description of the invention
Fig. 1 is cladding layer cross-sectional metallographic figure of the invention；
Fig. 2 is cladding layer cross section microhardness distribution figure of the invention；
Fig. 3 is clad layer surface conductivity figure of the invention.
Specific embodiment
Below by specific embodiment, the present invention is described in detail.
Embodiment 1:
A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method, comprising the following steps:
Preparing Ceramic Composite enhances cladding powder, and the amount of each component is by weight percentage are as follows: 5%ZrO2Powder, 5%Ni packet B4C Powder, 90%Cu powder；It is put into V-type batch mixer after accurately weighing above-mentioned powder, is stirred 2 hours with the revolving speed of 15r/min, then will be melted Whiting end is put into drying box, and 1h is dried at 120 DEG C, is removed the moisture in powder, is obtained cladding powder.
Fine copper matrix surface to cladding pre-processes, using sand paper polishing to cladding fine copper matrix, with remove surface blot, Oxide；The surface to cladding fine copper matrix is wiped using dehydrated alcohol；Using hairbrush in one layer of carbon ink of fine copper external coating Water is put into drying box, the dry 10min at 120 DEG C.
The cladding apparatus chosen in the present embodiment includes 1.064 μm of semiconductor light fibre laser, numerically-controlled machine tool and paraxonic Powder feeder, the size of fine copper matrix are 50 × 150 × 15mm3, using fixture by fine copper matrix be fixed on numerically-controlled machine tool and with The speed of 1mm/s is mobile, is first 1400W by the power setting of laser, irradiates 6min to fine copper matrix surface, make pure to cladding Copper substrate surface temperature reaches 500 DEG C.It is again 1800W, overlapping rate 50%, while paraxonic powder feeding by the power setting of laser Ceramic Composite enhancing cladding powder is sent at LASER SPECKLE by device, and loads powder gas is argon gas, and throughput 2L/min, powder sending quantity is 1g/min.Form ZrO2-B4C ceramics enhance cladding layer.
After fine copper matrix is air-cooled to room temperature after cladding, sample is cut into required size using electro-spark cutting machine and is carried out Test, the average microhardness of cladding layer cross section is about 111HV as the result is shown0.2, conductivity 60.5IACS%.
Wherein prepare the sequence interchangeable of the surface preparation of cladding powder and fine copper matrix.
Embodiment 2:
A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method, comprising the following steps:
Preparing Ceramic Composite enhances cladding powder, and the amount of each component is by weight percentage are as follows: 10%ZrO2Powder, 10%Ni packet B4C powder, 80%Cu powder；It is put into V-type batch mixer after accurately weighing above-mentioned powder, with revolving speed stirring 2 hours of 15r/min, then Cladding powder is put into drying box, 1h is dried at 120 DEG C, the moisture in powder is removed, obtains cladding powder.
The surface preparation of fine copper matrix to cladding, using sand paper polishing to cladding fine copper matrix, to remove surface dirt Stain, oxide；The surface to cladding fine copper matrix is wiped using dehydrated alcohol；Using hairbrush in one layer of carbon of fine copper external coating Ink is put into drying box, the dry 10min at 120 DEG C.
The cladding apparatus chosen in the present embodiment includes 1.064 μm of semiconductor light fibre laser, numerically-controlled machine tool and paraxonic Powder feeder, the size of fine copper matrix are 50 × 150 × 15mm3, using fixture by fine copper matrix be fixed on numerically-controlled machine tool and with The speed of 2mm/s is mobile, is first 1500W by the power setting of laser, irradiates 6min to fine copper matrix surface, make pure to cladding Copper substrate surface temperature reaches 500 DEG C.It is again 2400W, overlapping rate 50%, while paraxonic powder feeding by the power setting of laser Ceramic Composite enhancing cladding powder is sent at LASER SPECKLE by device, and loads powder gas is argon gas, and throughput 4L/min, powder sending quantity is 2g/min.Form ZrO2-B4C ceramics enhance cladding layer.
After fine copper matrix is air-cooled to room temperature after cladding, sample is cut into required size using electro-spark cutting machine and is carried out Test, the average microhardness of cladding layer cross section is 173HV as the result is shown0.2, conductivity 45.7IACS%.
Wherein prepare the sequence interchangeable of the surface preparation of cladding powder and fine copper matrix.
Embodiment 3:
A kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method, comprising the following steps:
Preparing Ceramic Composite enhances cladding powder, and the amount of each component is by weight percentage are as follows: 10%ZrO2Powder, 20%Ni packet B4C powder, 70%Cu powder；It is put into V-type batch mixer after accurately weighing above-mentioned powder, with revolving speed stirring 2 hours of 15r/min, then Cladding powder is put into drying box, 1h is dried at 120 DEG C, the moisture in powder is removed, obtains cladding powder.
The surface preparation of fine copper matrix to cladding, using sand paper polishing to cladding fine copper matrix, to remove surface dirt Stain, oxide；The surface to cladding fine copper matrix is wiped using dehydrated alcohol；Using hairbrush in one layer of carbon of fine copper external coating Ink is put into drying box, the dry 10min at 120 DEG C.
The cladding apparatus chosen in the present embodiment includes 1.064 μm of semiconductor light fibre laser, numerically-controlled machine tool and paraxonic Powder feeder, the size of fine copper matrix are 50 × 150 × 15mm3, using fixture by fine copper matrix be fixed on numerically-controlled machine tool and with The speed of 2mm/s is mobile, is first 1600W by the power setting of laser, irradiates 5min to fine copper matrix surface, make pure to cladding Copper substrate surface temperature reaches 500 DEG C.It is again 2200W, overlapping rate 50%, while paraxonic powder feeding by the power setting of laser Ceramic Composite enhancing cladding powder is sent at LASER SPECKLE by device, and loads powder gas is argon gas, and throughput 6L/min, powder sending quantity is 4g/min.Form ZrO2-B4C ceramics enhance cladding layer.
After fine copper matrix is air-cooled to room temperature after cladding, sample is cut into required size using electro-spark cutting machine and is carried out Test, the average microhardness of cladding layer cross section is 206HV as the result is shown0.2, conductivity 32.7IACS%.
Wherein prepare the sequence interchangeable of the surface preparation of cladding powder and fine copper matrix.
Zirconium dioxide (ZrO2) have the characteristics that low, anti-oxidant, the heat-resisting erosion of thermal conductivity, chemical property are stablized, it can drop Low friction towards Copper substrate heat transmitting, improve the operating temperature of matrix, under high-temperature work environment using more.Boron carbide (B4C) have the characteristics that high rigidity, high-melting-point, high-wearing feature, in laser cladding process, boron, carbon (B, C) can be solid-solution in copper again In, so that the performance of cladding layer is significantly improved.Fig. 1 is the metallograph of cladding layer, it can be seen that needle-shaped and block-like enhancing Phase.Fig. 2 is cladding layer cross section microhardness distribution figure, and embodiment 1 melts under the conditions of enhancing phase material additive amount is lower The microhardness of coating about promotes 2 times, and cladding layer internal component is uniform.The cladding layer cross section of embodiment 3 is average micro- hard Spend highest, about the 4 of Copper substrate times.Fig. 3 is clad layer surface conductivity figure, it can be seen that the addition least embodiment of ceramic material 1 conductivity highest adds more ceramic material since the electric conductivity of ceramic material is poor, will affect copper-based Ceramic Composite The conductivity of material.
To sum up, in the above embodiment of the present invention, comprehensively consider hardness and conductivity, embodiment 2 is preferred plan.
The various embodiments described above can be subject to several variations in the case where not departing from protection scope of the present invention, therefore above illustrate to be wrapped Contain and structure shown in the drawings should be regarded as illustrative, rather than the protection scope to limit the present patent application patent.

Claims (7)

1. a kind of fine copper surface laser cladding prepares zirconium dioxide-boron carbide enhancing cladding layer method, which is characterized in that described Method the following steps are included:
A: preparation Ceramic Composite enhances cladding powder；The amount percentage by weight of each component in the Ceramic Composite enhancing cladding powder Than are as follows: 5~10%ZrO2Powder, 5~20%Ni packet B4C powder, surplus are Cu powder；The ZrO2Powder and Ni packet B4The mass ratio of C powder is 1:1~2；The ZrO2The granularity of powder is 25~48 μm, purity 99.9%；The Ni packet B4The granularity of C is 25~48 μm, B4C Content is 60wt.%；The granularity of the Cu powder is 53~75 μm, purity 99.9%；
B: the surface preparation of the fine copper matrix to cladding；
C: using synchronous powder feeding system mode, using laser cladding apparatus, makes Ceramic Composite enhancing cladding powder in the table of fine copper matrix The rapid consolidation in face forms ceramics enhancing cladding layer；
D: the fine copper matrix after cladding is air-cooled to room temperature；
The wherein sequence interchangeable of step A and step B.
2. a kind of fine copper surface laser cladding according to claim 1 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the specific preparation method of the Ceramic Composite enhancing cladding powder is, by each raw material powder according to described The full and uniform mixing of percentage, is then placed in drying box, dries 1h at 120 DEG C, obtains Ceramic Composite enhancing cladding powder.
3. a kind of fine copper surface laser cladding according to claim 2 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the full and uniform mixed specific method of raw material powder is that, using V-type batch mixer, speed of agitator is 15r/min, incorporation time 2h.
4. a kind of fine copper surface laser cladding according to claim 1 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the step B the following steps are included:
B1: the fine copper matrix using sand paper polishing to cladding, to remove surface blot, oxide；
B2: the surface using dehydrated alcohol wiping to the fine copper matrix of cladding；
B3: in one layer of carbon black ink of external coating of fine copper matrix, being put into drying box, the dry 10min at 120 DEG C.
5. a kind of fine copper surface laser cladding according to claim 1 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the laser cladding apparatus in step C includes laser, movable fixture and paraxonic powder feeder, institute The semiconductor light fibre laser that laser is 1.064 μm is stated, laser power is 1800~2200W, and overlapping rate is 30~50%；Institute Movable fixture is stated for fixing fine copper matrix, and movement speed is 1~2mm/s；The paraxonic powder feeder increases Ceramic Composite Strong cladding powder is sent at LASER SPECKLE, and load powder gas is argon gas, and throughput is 2~6L/min, and powder sending quantity is 1~2g/min.
6. a kind of fine copper surface laser cladding according to claim 5 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the fine copper matrix also needs to carry out the pre-heat treatment before carrying out laser melting coating, makes the fine copper to cladding Matrix surface temperature reaches 500 DEG C.
7. a kind of fine copper surface laser cladding according to claim 6 prepares zirconium dioxide-boron carbide enhancing cladding layer Method, which is characterized in that the specific method of the pre-heat treatment is, according to the size of fine copper matrix, using 1400~ 5~6min is irradiated to fine copper matrix surface under the low power laser of 1600W.
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CN109097620B (en) * 2018-09-05 2020-06-26 燕山大学 Laser additive manufacturing La2O3Method for preparing (Cu, Ni) gradient functional composite material
CN110819980B (en) * 2019-10-18 2021-04-06 山东大学 In situ generation of ZrB2ZrC-based cladding material, composite coating and preparation method
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