阅读说明：本技术 一种采用红外激光制造Cu基合金熔覆层的方法 (Method for manufacturing Cu-based alloy cladding layer by adopting infrared laser ) 是由 陈源 孙学熙 胡可欣 杨晓红 程志伟 于 2021-08-06 设计创作，主要内容包括：本发明涉及一种采用红外激光制造Cu基合金熔覆层的方法,包括以纳米增强材料为沉积基体,先在其表面进行化学镀铜处理,接着再化学镀上高红外吸收率的金属层,以获得多层包覆型的Cu基合金粉末；以普通红外激光作为热源,将多层包覆型的Cu基合金粉末采用同轴送粉激光熔覆技术,制备获得Cu基合金熔覆层。本发明旨在提出一种可在金属构件表面采用红外激光加工制造Cu基合金熔覆层的技术方案。(The invention relates to a method for manufacturing a Cu-based alloy cladding layer by adopting infrared laser, which comprises the steps of taking a nano reinforced material as a deposition matrix, carrying out chemical copper plating treatment on the surface of the deposition matrix, and then chemically plating a metal layer with high infrared absorption rate to obtain multilayer cladding Cu-based alloy powder; and (3) preparing the Cu-based alloy cladding layer by taking common infrared laser as a heat source and adopting a coaxial powder feeding laser cladding technology for the multilayer cladding type Cu-based alloy powder. The invention aims to provide a technical scheme for manufacturing a Cu-based alloy cladding layer on the surface of a metal component by adopting infrared laser processing.)

1. A method for manufacturing a Cu-based alloy cladding layer by adopting infrared laser is characterized by comprising the following steps: the method comprises the steps of taking a nano reinforced material as a deposition matrix, carrying out chemical copper plating treatment on the surface of the deposition matrix, and then chemically plating a metal layer with high infrared absorption rate to obtain multilayer coated Cu-based alloy powder;

and (3) preparing the Cu-based alloy cladding layer by taking common infrared laser as a heat source and adopting a coaxial powder feeding laser cladding technology for the multilayer cladding type Cu-based alloy powder.

2. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 1, wherein: the preparation method of the multilayer cladding type Cu-based alloy powder comprises the following steps:

s1: purifying the deposition matrix by nitric acid and hydrofluoric acid in sequence;

s2: SnCl treated purified deposition matrix₂Sensitizing by using HCl solution;

s3: the sensitized deposition substrate is subjected to PdCl₂Activating treatment by using HCl solution;

s4: adding the activated deposition matrix into a copper plating solution for chemical copper plating treatment to obtain chemical copper plating powder;

s5: and adding the copper-plated powder into the metal plating solution with high infrared absorption rate again for chemical plating coating treatment, and then cleaning for multiple times, taking out, drying, grinding and screening to obtain the multilayer coated Cu-based alloy powder.

3. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 2, wherein: the purification processing method in step S1 is as follows:

adding the deposition matrix and 68% nitric acid into a centrifugal tube, immersing the deposition matrix by the 68% nitric acid, covering a centrifugal tube cover, standing for 24h, centrifuging, pouring the nitric acid, replacing and pouring 40% hydrofluoric acid to immerse the deposition matrix again, standing for 24h, centrifuging again, pouring the hydrofluoric acid, and adding deionized water for multiple times for cleaning.

4. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 3, wherein: the sensitization processing method of the step S2 is as follows:

adding the deposition matrix subjected to S1 purification treatment to 0.1mol/L SnCl₂And (3) carrying out ultrasonic vibration treatment for 0.5-1h in a mixed solution of +0.1mol/L HCl, standing for 24h, centrifuging again, removing redundant solution and washing for multiple times.

5. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 4, wherein: the activation processing method of step S3 is as follows:

adding the deposition matrix sensitized by S2 into 0.0014mol/L SnCl₂And (3) carrying out ultrasonic vibration treatment for 0.5-1h in a mixed solution of +0.25mol/L HCl, standing for 24h, centrifuging again, removing redundant solution and washing for multiple times.

6. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 5, wherein: the copper plating solution in the step S4 comprises the following components in parts by weight:

30-40 parts of copper sulfate pentahydrate;

70-80 parts of disodium ethylene diamine tetraacetate dihydrate;

30-40 parts of 85% hydrazine hydrate solution;

the reaction temperature of the step S4 is 40-50 ℃, and the reaction time is 12-24h until the blue color in the copper plating solution becomes light or completely fades.

7. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 6, wherein: the metal with high infrared absorptivity is one of Fe, Ni, Co and Cr.

8. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 7, wherein: the infrared laser is semiconductor laser or optical fiber laser with the wavelength of 900-1080 nm.

9. The method for manufacturing the Cu-based alloy cladding layer by using the infrared laser as claimed in claim 8, wherein: the grain diameter of the multilayer cladding type Cu-based alloy powder is 10-150 mu m.

10. The method for manufacturing a Cu-based alloy cladding layer using an infrared laser according to any one of claims 1 to 9, wherein: the nano reinforcing material is one of carbon nano tube, graphene and C60 nano materials.

Technical Field

The invention relates to the field of metal material preparation, in particular to a method for manufacturing a Cu-based alloy cladding layer by adopting infrared laser.

Background

Laser cladding technology-a new material preparation technology using high energy laser beam to make additive manufacturing. The method is characterized in that a focused high-energy laser beam is used as a heat source to melt metal powder particles which are originally paved on the surface of a metal base material or are coaxially fed in real time to form a molten pool. After the laser beam is removed, the molten pool is rapidly solidified to form the additive manufacturing alloy layer. The laser cladding technology can prepare materials with special functions on the surface of a common base material: such as a stronger, harder, hard and wear resistant, more corrosion resistant, more conductive alloy layer, etc., to increase the service life of the metal member or to meet specific service requirements.

Cu and its alloys are one of the oldest and most widely used metal and alloy systems. Since Cu and its alloy have high conductivity, it is widely used in cable and other conductive members. Meanwhile, the Cu-based alloy can form a layer of compact passive film on the surface, and has a huge application prospect in marine corrosion prevention. However, Cu alloys have a relatively weak specific strength as compared with Fe-based, Ni-based, and Ti-based alloys, and thus have limited large-area applications. Therefore, the method for preparing the surface cladding layer of the Cu and the Cu alloy by deposition on the main bearing structural parts such as Fe, Ni, Ti and the like is an optimized scheme for combining the performances of the two metal structural parts, and has the realization requirements in electric conduction and marine corrosion prevention.

Compared with other surface coating deposition technologies, the laser cladding technology has the technical characteristics of open preparation environment, simple process, metallurgical bonding with a matrix, compact forming and the like, and is very suitable for preparing Cu and an alloy layer thereof. However, the laser heat source used at present is mainly semiconductor laser, fiber laser, or semiconductor-coupled fiber laser, which has a wavelength of 900-. And Cu and its alloy are just the lowest laser absorption materials in this band. Therefore, the common infrared laser is adopted to process the cladding layer of Cu and the base alloy, the difficulty is very high, and even the technology is not feasible at all. Therefore, in recent years, laser in green and blue light bands has been developed on the basis of infrared laser, and laser cladding manufacturing of Cu and base alloys is mainly performed. However, at present, the cost of green and blue lasers is always high, reaching millions to tens of millions, and cannot be borne by general enterprises, and the popularization difficulty of application is large.

Therefore, how to prepare the cladding layer of Cu and its alloy on the surface of the metal component by using the ordinary infrared laser still has a great demand in practical application, and needs to make a breakthrough in process and technology.

Disclosure of Invention

In view of the above problems in the prior art, the present invention aims to overcome the disadvantages in the prior art, and to provide a technical solution for manufacturing a Cu-based alloy cladding layer on the surface of a metal component by using infrared laser processing.

The method for manufacturing the Cu-based alloy cladding layer by adopting the infrared laser comprises the steps of taking a nano reinforcing material as a deposition matrix, carrying out chemical copper plating treatment on the surface of the deposition matrix, and then chemically plating a metal layer with high infrared absorption rate to obtain multilayer cladding type Cu-based alloy powder;

and (3) preparing the Cu-based alloy cladding layer by taking common infrared laser as a heat source and adopting a coaxial powder feeding laser cladding technology for the multilayer cladding type Cu-based alloy powder.

By adopting the technical scheme: the nano reinforced material is used as the precipitation matrix, so that the final performance of the finally prepared powder has a reinforced effect. The surface of the precipitation matrix is plated with a layer of metal copper and then a layer of metal layer with high infrared absorption rate, so that a double-layer alloy is formed on the surface of the precipitation matrix. It is to be emphasized that: the multilayer cladding Cu-based alloy powder prepared by the method is applied to the field of laser cladding, and copper is an element with the highest infrared laser reflectivity, so that the copper is used for protecting a precipitation matrix from being damaged in the laser processing process. However, if the infrared laser is reflected, the powder cannot be melted, and the purpose of laser cladding cannot be achieved, so that a metal layer with good laser absorption rate is further coated on the outer surface of the copper to form a cladding layer applicable to laser cladding. Secondly, the multilayer cladding Cu-based alloy powder prepared by the method has good fluidity and can be suitable for coaxial powder feeding cladding with higher requirements on powder fluidity. The Cu-based alloy cladding layer can be manufactured on the surface of a metal component by adopting common infrared laser processing.

Further, the preparation method of the multilayer cladding type Cu-based alloy powder comprises the following steps:

s1: purifying the deposition matrix by nitric acid and hydrofluoric acid in sequence;

s2: SnCl treated purified deposition matrix₂Sensitizing by using HCl solution;

s3: the sensitized deposition substrate is subjected to PdCl₂Activating treatment by using HCl solution;

s4: adding the activated deposition matrix into a copper plating solution for chemical copper plating treatment to obtain chemical copper plating powder;

s5: and adding the copper-plated powder into the metal plating solution with high infrared absorption rate again for chemical plating coating treatment, and then cleaning for multiple times, taking out, drying, grinding and screening to obtain the multilayer coated Cu-based alloy powder.

By adopting the technical scheme: sequentially carrying out purification, sensitization and activation treatment on the surface of the deposition matrix, wherein: the purification is to remove impurities in the initial carbon nanotube production and form a small amount of oxidized groups on the surface of the carbon nanotube; sensitization is to attach Sn2+ ions on the surface of the carbon nano tube; the activation is to reduce Pd2+ ions into Pd elemental particles by Sn2+ ions, and the Pd elemental particles are used as nucleation particles on the surface of the deposition substrate in electroless plating.

Further, the purification processing method in step S1 is as follows:

adding the deposition matrix and 68% nitric acid into a centrifugal tube, immersing the deposition matrix by the 68% nitric acid, covering a centrifugal tube cover, standing for 24h, centrifuging, pouring the nitric acid, replacing and pouring 40% hydrofluoric acid to immerse the deposition matrix again, standing for 24h, centrifuging again, pouring the hydrofluoric acid, and adding deionized water for multiple times for cleaning.

Further, the sensitization processing method of step S2 is as follows:

adding the deposition matrix subjected to S1 purification treatment to 0.1mol/L SnCl₂And (3) carrying out ultrasonic vibration treatment for 0.5-1h in a mixed solution of +0.1mol/L HCl, standing for 24h, centrifuging again, removing redundant solution and washing for multiple times.

Further, the activation processing method of step S3 is as follows:

adding the deposition matrix sensitized by S2 into 0.0014mol/L SnCl₂And (3) carrying out ultrasonic vibration treatment for 0.5-1h in a mixed solution of +0.25mol/L HCl, standing for 24h, centrifuging again, removing redundant solution and washing for multiple times.

Further, the copper plating solution in the step S4 includes the following components in parts by weight:

30-40 parts of copper sulfate pentahydrate;

70-80 parts of disodium ethylene diamine tetraacetate dihydrate;

30-40 parts of 85% hydrazine hydrate solution;

the reaction temperature of the step S4 is 40-50 ℃, and the reaction time is 12-24h until the blue color in the copper plating solution becomes light or completely fades.

By adopting the technical scheme: the chemical copper plating solution adopts disodium ethylene diamine tetraacetic acid dihydrate as a chelating agent, and hydrazine hydrate as a reducing agent to reduce copper ions in the plating solution into a metal simple substance, thereby realizing chemical copper plating. In addition, the reaction process only needs to be slightly heated (40 ℃), so that the energy consumption is low. In step S4, the solution that has reacted completely may be poured out after the completion of one-time chemical plating, and after the replacement with a new plating solution, the chemical plating reaction may be restarted, so that the deposition amount of Cu metal may be increased by multiple times of chemical plating; in addition, alloy powder with different coating thicknesses and different Cu alloy mass ratios can be obtained through the process parameters of the concentration of Cu ions of the chemical plating solution, the using amount of the plating solution, the plating time, the plating times and the like.

Further, the metal with high infrared absorptivity is one of Fe, Ni, Co and Cr.

By adopting the technical scheme: when the metal plating solution with high infrared absorption rate is selected, the metals such as Fe, Ni, Co, Cr and the like which are easy to deposit by chemical plating and have high infrared laser absorption rate are mainly selected.

During specific preparation, the copper-plated powder can be added into chemical plating solutions of Fe/Ni/Co/Cr and the like again for chemical plating treatment, and then the copper-plated powder is cleaned for multiple times, dried and screened to obtain multilayer coated Cu-based alloy powder;

furthermore, the infrared laser is a semiconductor laser or a fiber laser with the wavelength of 900-1080 nm.

By adopting the technical scheme: the cladding layer is prepared by adopting a coaxial powder feeding laser cladding technology to obtain better matrix combination and alloy formability.

Further, the particle size of the multilayer cladding type Cu-based alloy powder is 10-150 μm.

By adopting the technical scheme: the obtained Cu-based alloy powder is multilayer metal type powder, and the powder particles can be adjusted according to actual working conditions through plating solution ion concentration, bottom application time, times and the like. And the particle size is controlled within the range of 10-150 mu m, so that the requirement of most additive manufacturing technologies on the particle size of the powder is covered.

Further, the nano reinforcing material is one of carbon nano tube, graphene and C60 nano material.

By adopting the technical scheme: the carbon nano tube, graphene or C60 nano material used as the initial deposition material is a nano reinforcing material, and the final performance of the alloy has a certain reinforcing effect. In addition, the initial deposition material is in a nanometer scale, so that ultrafine powder particles in a dozen to hundreds of nanometer scales can be obtained through process control, powder particles in a dozen to one hundred micrometers can be obtained through continuous deposition of Cu alloy metal particles in multiple times of chemical plating, and the requirement of most additive manufacturing technologies on the powder particle size is covered.

To sum up, the application comprises the following beneficial technical effects:

1. the invention provides a method for manufacturing a Cu-based alloy cladding layer by adopting infrared laser, which prepares multilayer cladding type Cu alloy powder by a special multilayer chemical plating method, avoids the technical problem of difficult material increase manufacturing caused by low infrared laser absorptivity of Cu, and can prepare and combine compact Cu-based alloy cladding layer by common and most common infrared laser to form good Cu-based alloy cladding layer. It is to be emphasized that: the multilayer coated Cu-based alloy powder prepared by the method has good fluidity and is suitable for coaxial powder feeding cladding with higher requirement on powder fluidity;

2. according to the method for preparing the coated Cu-based alloy powder by the chemical plating method, the powder preparation process only needs common laboratory equipment such as an ultrasonic cleaning machine, a centrifugal machine, a magnetic stirrer, a water bath heater, a beaker and the like, and does not need high equipment investment;

3. the preparation method of the multilayer coated Cu-based alloy powder provided by the invention is characterized in that Cu and other metal ions in chemical plating solution are reduced into metal simple substances by utilizing the reduction action of a chemical reducing agent, the manufacturing process only needs to slightly heat (40-60 ℃), and the energy consumption is low.

4. The method can quickly and conveniently regulate and control the components of the alloy by changing the control of parameters such as ion concentration, plating time, plating frequency and the like of the chemical plating solution, and meet the requirements of different applications;

5. the initial carbon nano-materials such as the carbon nano-tube, the graphene, the C60 and the like are nano reinforced materials with excellent mechanical properties and have extremely high conductive properties, so that the Cu-based alloy prepared by the method can obtain a composite alloy layer with better strength and better conductive property by regulating and controlling the carbon nano-materials.

Drawings

FIG. 1 is an SEM microtopography of an initial deposition material using multi-walled carbon nanotubes according to an embodiment of the present invention;

FIG. 2 is an SEM micro-morphology of NiCu alloy powder obtained by chemical plating according to an embodiment of the present invention;

FIG. 3 is a cross-sectional view of a laser cladding layer of NiCu alloy obtained according to an embodiment of the present invention;

FIG. 4 is an EDS spectrum and analysis results of a laser cladding layer of NiCu alloy obtained in the example of the present invention.

Detailed Description

The present application is described in further detail below with reference to figures 1-4.

The embodiment of the application discloses a method for manufacturing a Cu-based alloy cladding layer by adopting infrared laser.

S1: selecting two 20mL plastic centrifuge tubes, weighing 0.1 g of multi-wall carbon nanotubes in each tube (the carbon nanotubes in the embodiment are prepared by a chemical catalysis method, the microcosmic outer diameter is 30-50nm, and the average length is about 10 μm); adding about 10mL of 68% nitric acid into each centrifugal tube to immerse the carbon nano tube, covering the tube cover and standing for 24h, centrifuging, pouring out the nitric acid, replacing and pouring about 10mL of 40% hydrofluoric acid to immerse the carbon nano tube again, standing for 24h, centrifuging again, pouring out the hydrofluoric acid, and adding deionized water for multiple times to clean.

S2: two 100mL beakers were added with 200mL of 0.1mol/L SnCl₂And adding 0.1mol/L HCl mixed solution into each beaker for every 0.1 g of the multi-walled carbon nano-tubes subjected to the S1 purification treatment, performing ultrasonic treatment for 0.5h, standing for 24h, centrifuging again, removing redundant solution, and cleaning for multiple times.

S3: 100-200mL of 0.0014mol/L SnCl is added into a beaker₂And adding 0.1 g of carbon nano tube subjected to S2 sensitization into the HCl mixed solution by +0.25mol/L, performing ultrasonic vibration treatment again for 0.5h, standing for 24h, centrifuging again, removing redundant solution, and cleaning for multiple times.

S4: adding 0.2 g of carbon nano tubes which are activated by S3 into chemical copper plating solution (the optimized formula of the plating solution is 70-80 g of disodium ethylene diamine tetraacetic acid dihydrate, 30-40 g of copper sulfate pentahydrate and 30-40mL of 85% hydrazine hydrate solution), setting the reaction temperature to be 50 ℃, reacting for 24h, and pouring out the chemical plating solution after the reaction is completed. In order to increase the deposition amount of Cu on the surface of the multi-walled carbon nanotube, the chemical plating treatment process of S4 is repeated for 1 time, namely, a new plating solution is replaced and poured, the chemical plating Cu reaction can be restarted, and then a thicker Cu plating layer is deposited on the surface of the carbon nanotube.

S5: adding the powder obtained by S4 electroless copper plating treatment into an electroless nickel plating solution (the optimized formula adopted in the embodiment is 70-80 g of sodium citrate dihydrate, 30-40 g of nickel chloride hexahydrate, 1-5 g of sodium hydroxide and 30-40mL of 85% hydrazine hydrate solution), setting the reaction temperature to be 60 ℃, setting the reaction time to be 12h, and pouring out the electroless plating solution after the reaction is completed.

And (2) adding clear water to clean the powder subjected to the chemical copper plating and nickel plating treatment of S4 and S5 for multiple times (because the thick bottom layer is deposited on the surface of the carbon nano tube and the density is increased due to multiple times of chemical plating, the powder can naturally sink to the bottom of the beaker only by adding the clear water and standing for a while in the cleaning process, pouring out the clear water on the upper layer, and repeating the steps for multiple times to achieve the aim of cleaning the powder).

Taking out the cleaned powder, and drying the powder at the temperature of 100-200 ℃; then putting the powder into a mortar for grinding; the ground powder is screened by a 100-sand 500-mesh sieve to obtain NiCu double-layer alloy powder with the required particle size range of 30-150 mu m.

FIG. 1 is an SEM micrograph of a multi-walled carbon nanotube as a starting material deposited by the example, which is prepared by a catalytic method, and has an outer diameter of 30-50nm and an average length of about 10 μm.

As shown in fig. 2, an SEM micro-morphology of the NiCu double-layer alloy powder obtained by the multiple chemical plating method in this embodiment can be seen, the powder is in a nearly spherical shape or a nearly ellipsoidal shape, the particle size of the powder is between 30 μm and 150 μm, and the actual measurement result shows that the powder has good fluidity, and meets the requirement of the coaxial powder feeding laser cladding processing.

As shown in fig. 3, in the embodiment, a nickel-based Inconel 718 alloy is used as a base material, a semiconductor-coupled fiber infrared laser beam is used as a heating source (laser LDM-3000 laser, wavelength 900-: the laser power is 1kW, the powder feeding speed is 1g/min, and the scanning speed is 2 mm/s. As can be seen, the cladding layer bonds well to the substrate, forming a complete metallurgical bond. Meanwhile, the internal structure of the cladding layer is compact, and obvious defects such as holes, cracks and the like do not exist. The method can be used for preparing and obtaining the Cu-based alloy cladding layer with high quality and good forming by utilizing common infrared laser.

FIG. 4 shows the EDS spectrum and the elemental analysis results of the NiCu laser cladding layer obtained in this example. It can also be seen from the data results that the Ni and Cu elements in the powder have melted into the melt pool and eventually solidified to form a Cu-based alloy cladding layer.

The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.