CN111185594B - Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding - Google Patents

Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding Download PDF

Info

Publication number
CN111185594B
CN111185594B CN202010100683.3A CN202010100683A CN111185594B CN 111185594 B CN111185594 B CN 111185594B CN 202010100683 A CN202010100683 A CN 202010100683A CN 111185594 B CN111185594 B CN 111185594B
Authority
CN
China
Prior art keywords
powder
nickel
composite powder
ceramic powder
coated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010100683.3A
Other languages
Chinese (zh)
Other versions
CN111185594A (en
Inventor
刘炜
曹玉
阴建能
王建宏
赵占勇
李忠华
白培康
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
North University of China
Original Assignee
North University of China
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by North University of China filed Critical North University of China
Priority to CN202010100683.3A priority Critical patent/CN111185594B/en
Publication of CN111185594A publication Critical patent/CN111185594A/en
Application granted granted Critical
Publication of CN111185594B publication Critical patent/CN111185594B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemically Coating (AREA)

Abstract

The invention discloses a preparation method of nickel-coated ceramic composite powder based on selective laser melting molding, which comprises the steps of firstly etching ceramic powder by using etching liquid composed of formic acid and hydrogen peroxide, then sensitizing and activating the etched ceramic powder according to a conventional method, and then placing the ceramic powder in chemical nickel plating liquid for reaction to obtain the nickel-coated ceramic composite powder with uniform plating. The nickel-coated ceramic composite powder prepared by the invention has uniform particle size distribution and high nickel-plated layer quality, and can be used for modifying cobalt-chromium alloy, and the cobalt-chromium alloy part is prepared by selective laser melting molding, so that the wear rate is lower than that of the common cobalt-chromium alloy, the hardness and the tensile strength are better than those of the common cobalt-chromium alloy, and the nickel-coated ceramic composite powder is suitable for serving as an orthopedic implant, in particular to an artificial hip joint prosthesis.

Description

Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding
Technical Field
The invention belongs to the technical field of composite powder modification for metal matrix composite materials, and relates to a preparation method of nickel-coated ceramic composite powder.
Background
The Selective Laser Melting molding (SLM) technology is based on a digital model file, and constructs a metal part by selectively Melting metal powder materials of each layer by a Laser beam through a software layered discrete and numerical control molding system and gradually stacking and molding the metal powder materials.
Compared with the traditional process, the selective laser melting molding 3D printing technology is adopted when the medical metal implant is prepared, and the personalized metal implant can be quickly and accurately customized according to different bone characteristics, so that the problems that the shape of the traditional universal metal implant is incompatible with an individual and the mechanical property does not reach the standard are solved; when complex structures and difficult-to-process products are manufactured, microstructures, particularly porous structures, are customized individually, and transportation of blood, nutrients, metabolic waste and the like and growth of bone tissues are facilitated.
The medical metal implant material mainly comprises stainless steel, cobalt-chromium alloy, titanium and titanium alloy, medical noble metal (tantalum, niobium and zirconium) and the like. The cobalt-chromium alloy has good thermal conductivity, high strength, high fracture toughness, hardness, corrosion resistance and biocompatibility, and is widely applied to the field of medical implants such as denture crowns, hip prosthesis replacement and the like. In particular to an artificial hip joint prosthesis which needs to support the load of the upper half of the human body and also has the functions of walking, moving and squatting of the human body, and the wear resistance of the cobalt-chromium alloy directly determines the service effect and the service life of the prosthesis.
The ceramic material has the advantages of high melting point, high hardness, high wear resistance, oxidation resistance and the like, and can obviously enhance the wear resistance of the cobalt-chromium alloy and prolong the service life of the cobalt-chromium alloy implant by compounding the ceramic material with the cobalt-chromium alloy.
However, because the surface wettability of the ceramic material and the cobalt-chromium alloy is greatly different, the ceramic powder and the cobalt-chromium alloy powder are directly mechanically mixed and then printed by using the SLM process, the stability of the internal structure and the interface cohesiveness of the product are poor, internal defects are easy to occur, and the mechanical performance of the material is reduced.
A nickel-plated layer is formed on the surface of the ceramic powder by a chemical nickel plating method to obtain nickel-coated ceramic composite powder, and the nickel-coated ceramic composite powder is mixed with cobalt-chromium alloy powder in proportion and then printed, so that a transition layer can be formed between the ceramic and the cobalt-chromium alloy, the wettability of the ceramic-metal surface is improved, and the mechanical property and the wear resistance of a printed part are improved.
CN 106623908A discloses a preparation method of micron-sized hexagonal boron nitride composite powder coated by chemical nickel plating, which adopts a traditional chemical nickel plating mode to form a coating on the surface of boron nitride, and has an obvious core-shell structure, but hexagonal boron nitride is easy to agglomerate in the nickel plating process, and the coating quality of the nickel coating is poor.
CN 109807324A discloses a method for preparing a nanoscale hexagonal boron nitride sheet coated by chemical nickel plating, which aims at the defect that boron nitride is easy to agglomerate in the nickel plating process, and adds materials such as a dispersing agent, a stabilizing agent, a complexing agent and the like to achieve a good dispersing effect.
Disclosure of Invention
The invention aims to provide a preparation method of nickel-coated ceramic composite powder based on selective laser melting molding, the composite powder prepared by the method has the advantages of high particle size distribution and nickel plating layer quality and uniform plating layer, and the composite powder can be mixed in cobalt-chromium alloy powder to prepare a high-wear-resistance cobalt-chromium alloy part by selective laser melting molding.
The preparation method of the nickel-coated ceramic composite powder based on selective laser melting molding comprises the steps of firstly etching the ceramic powder by using etching liquid composed of formic acid and hydrogen peroxide, then sensitizing and activating the etched ceramic powder according to a conventional method, and placing the ceramic powder in chemical nickel plating liquid for reaction to obtain the nickel-coated ceramic composite powder with uniform plating.
Further, the invention provides a more specific preparation method of the nickel-coated ceramic composite powder based on selective laser melting molding.
1) Mixing formic acid and hydrogen peroxide in a volume ratio of (5-10) to 1 to obtain etching liquid, and adding ceramic powder to perform surface etching to obtain etched ceramic powder.
2) And adding the etched ceramic powder into stannous chloride sensitizing solution, and carrying out sensitization treatment to obtain sensitized ceramic powder.
3) And adding the sensitized ceramic powder into a palladium chloride activating solution for activation treatment to obtain activated ceramic powder.
4) And placing the activated ceramic powder in chemical nickel plating solution with the pH value of 11-13, and reacting for 0.5-2 h at 40-80 ℃ to obtain the uniformly plated nickel-coated ceramic composite powder.
The nickel-coated ceramic composite powder prepared by the preparation method has uniform coating, the particle size of nickel particles is 10-100 nm, and the particle size of the composite powder is mainly about 50 mu m.
The ceramic powder of the present invention includes, but is not limited to, oxide and carbide ceramic powders such as alumina, zirconia, mullite, silicon carbide and boron carbide.
In the preparation method, the etching, sensitizing and activating treatment time is preferably 30-50 min, and stirring treatment is assisted in the treatment process.
Specifically, the sensitizing solution used in the preparation method comprises 10-40 g/l of stannous chloride, 20-60 ml/l of concentrated hydrochloric acid and the balance of deionized water; the activating solution contains 0.1-1 g/l of palladium chloride, 5-15 ml/l of concentrated hydrochloric acid and the balance of deionized water.
Further, the chemical nickel plating solution of the invention comprises the following components: 10-40 g/l of nickel sulfate hexahydrate, 30-60 ml/l of hydrazine hydrate, 30-90 g/l of sodium citrate, 10-50 ml/l of boric acid, 10-100 mg/l of PVP and the balance of deionized water.
Preferably, in the chemical nickel plating process, the invention is assisted with a treatment means of ultrasonic pulverization to inhibit the agglomeration of ceramic powder and make the nickel coating more uniform.
In fact, the ultrasonic pulverization treatment is already a conventional treatment method, and the present invention can adopt any one of the conventional ultrasonic treatment methods, for example, a cell pulverizer, a high-power ultrasonic cleaner, and the like.
In the preparation method, various ceramic powders after different treatments, including ceramic powders after etching, sensitization, activation and nickel plating, need to be cleaned and dried. Specifically, the cleaning is performed for 2-4 times by using deionized water, and then the cleaning is performed for 1-3 times by using absolute ethyl alcohol.
Further, the ceramic powder after cleaning is dried at 60 to 80 ℃ for 0.5 to 2 hours.
Furthermore, the adding amount of the ceramic powder in the etching liquid is preferably 30-60 g/l.
Furthermore, the adding amount of the ceramic powder in the sensitizing solution and the activating solution is preferably 10-50 g/l.
The invention preferably cleans the prepared nickel-coated ceramic composite powder and then carries out vacuum freeze drying.
The nickel-coated ceramic composite powder prepared by the method is used for being mixed into cobalt-chromium alloy powder to modify the cobalt-chromium alloy.
Specifically, the mixing amount of the nickel-coated ceramic composite powder is 0.5-3% of the mass of the cobalt-chromium alloy powder.
The wear rate of the cobalt-chromium alloy part prepared by using the cobalt-chromium alloy modified by the nickel-coated ceramic composite powder and adopting the selective laser melting forming process is lower than that of the common cobalt-chromium alloy, and the hardness and tensile strength of the cobalt-chromium alloy part are better than those of the common cobalt-chromium alloy part.
According to the invention, the etching solution composed of formic acid and hydrogen peroxide is used for etching the surface of the ceramic powder, on one hand, hydrogen peroxide has strong oxidizability, and oil stains have unsaturated bonds, and the reaction is carried out between the hydrogen peroxide and the oil stains, so that the oil stains are denatured into soluble substances, and the oil removing effect is achieved; on the other hand, the performic acid is generated after the formic acid and the hydrogen peroxide are mixed, the higher corrosivity is realized, the surface of the deoiled ceramic powder is further etched, the specific surface area of the ceramic powder is increased, and the plating quality of a nickel layer is favorably improved.
The invention utilizes ultrasonic pulverization treatment to disperse ceramic powder in the chemical nickel plating process, and higher ultrasonic frequency inhibits the agglomeration of the ceramic powder, so that the ceramic powder can be uniformly dispersed in the plating solution, the contact between the plating solution and the surface of the ceramic powder is promoted, and the reaction speed is accelerated. Furthermore, the nickel-coated ceramic composite powder is subjected to vacuum freeze drying, so that the agglomeration of the ceramic powder caused by water evaporation in the drying process is prevented, and the nickel-coated ceramic composite powder with uniform particle size distribution is finally obtained.
The nickel-coated ceramic composite powder prepared by the method is mixed with cobalt-chromium alloy powder in proportion, and then the cobalt-chromium alloy part is prepared by using a selective laser melting molding process, so that the hardness and the wear resistance of the part can be effectively improved, and the nickel-coated ceramic composite powder is suitable for serving as an orthopedic implant material, in particular to an artificial hip joint prosthesis.
Drawings
FIG. 1 is a drawing for etching Al2O3Powder and unetched Al2O3The nitrogen adsorption-desorption curves of the powders are compared.
FIG. 2 shows non-etched Ni-clad Al2O3Energy spectrum of the composite powder.
FIG. 3 shows Ni-coated Al2O3Energy spectrum of the composite powder.
FIG. 4 shows non-etched Ni clad Al2O3Composite powder and Ni-coated Al2O3XRD comparison pattern of composite powder.
FIG. 5 shows Ni-coated Al2O3SEM image of the composite powder.
FIG. 6 shows Ni-coated Al2O3High power SEM image of composite powder.
Detailed Description
The following examples further describe embodiments of the present invention. The following examples are only for illustrating the technical solutions of the present invention more clearly, and do not limit the scope of the present invention. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.
Example 1.
Taking 35ml of formic acid and 4ml of 30% hydrogen peroxide, and uniformly mixing to obtain the etching solution.
2g of Al was added to the etching solution2O3Magnetically stirring the powder for 30min, filtering, washing with deionized water for 2 times, washing with anhydrous ethanol for 1 time, and oven drying at 65 deg.C for 2 hr to obtain etched Al2O3And (3) powder.
1g of stannous chloride dihydrate is weighed and dissolved in 2ml of concentrated hydrochloric acid, and the volume is fixed to 50ml by deionized water to obtain the sensitizing solution.
0.025g of palladium chloride is weighed, dissolved in 0.5ml of concentrated hydrochloric acid, and the volume is adjusted to 50ml by deionized water, so as to obtain the activation solution.
Etching Al2O3Placing the powder in sensitizing solution, magnetically stirring for 30min, centrifuging, washing with deionized water for 2 times, and washing with anhydrous ethanol for 1 time to obtain sensitized Al2O3And (3) powder.
Finally, sensitizing Al2O3Placing the powder in activating solution, magnetically stirring for 30min, centrifuging, washing with deionized water for 2 times, washing with anhydrous ethanol for 1 time, and oven drying at 65 deg.C for 2 hr to obtain activated Al2O3And (3) powder.
Weighing 1.25g of nickel sulfate hexahydrate, 2.5g of sodium citrate, 1.5g of boric acid and 1.25mg of PVP, adding into deionized water, stirring and dissolving, adding 2.5ml of hydrazine hydrate, and fixing the volume to 50ml with the deionized water to prepare the chemical plating solution.
Adjusting the pH of the electroless plating solution to 13, adding the activated Al2O3Placing the powder in a cell crusher, and reacting for 0.5h at 50 ℃.
After the reaction is finished, standing and separating out a reaction product, washing for 3 times by using deionized water and 2 times by using absolute ethyl alcohol, and freeze-drying until the reaction product is dried to obtain the Ni-coated Al with uniform plating2O3And (3) compounding the powder.
Comparative example 1.
Weighing 2g of Al2O3Powder, which was sensitized and activated without etching by the method of example 1, was placed in electroless plating solution to react to obtain non-etched Ni-coated Al2O3Composite powder, which served as a control.
FIG. 1 shows etched Al prepared in example 1 above2O3Powder and non-etched Al2O3Nitrogen adsorption-desorption profile of the powder. As can be seen from the figure, Al is etched2O3The specific surface area of the powder is obviously larger than that of the non-etched Al2O3Powder, which is advantageous in increasing Al per unit mass during electroless Ni plating2O3The number of Ni atoms plated on the powder surface.
FIGS. 2 and 3 show Ni-coated Al prepared in example 12O3Composite powder and comparisonEXAMPLE 1 preparation of non-etched Ni-clad Al2O3Energy spectrum of the composite powder. According to the comparative data, compared with the comparative example, the Ni content plated on the surface of the composite powder subjected to etching treatment in the example 1 is remarkably increased, and the high-density workpiece can be obtained in the subsequent selective laser melting forming process.
FIG. 4 shows preparation of Ni-coated Al in example 12O3Composite powder and comparative example 1 preparation of non-etched Ni-coated Al2O3XRD pattern of the composite powder. It can be seen that Al is not the main component2O3Whether the powder is etched or not, and Ni and Al exist in the prepared composite powder2O3Two phases, demonstrated in Al2O3Metallic Ni is formed on the powder surface.
FIG. 5 shows preparation of Ni-clad Al in example 12O3Scanning electron micrographs of the composite powder. As shown in the figure, Ni atoms are uniformly coated on Al2O3A surface. Further, Ni-coated Al was prepared according to example 1 of FIG. 62O3In the high-power scanning electron microscope image of the composite powder, it can be seen that the particle size of the Ni particles is 50nm or less.
Example 1 is applied.
Ni-clad Al prepared in example 12O3Composite powder and non-etched Ni-coated Al prepared in comparative example 12O3The composite powder is mixed in cobalt-chromium alloy powder according to a certain proportion, and a selective laser melting forming process is adopted to prepare a cobalt-chromium alloy part with a specific shape on a stainless steel substrate.
The selected area laser melting equipment selected in the experiment is Renyshao AM400, and the laser is a fiber laser. The specific selective laser melting forming process comprises the following steps: laser power 198W, scanning speed 874mm/s, scanning line spacing 0.04mm, and powder laying thickness 0.03 mm.
The experiment was conducted with 5 groups, wherein group 1 was pure cobalt-chromium alloy powder without any composite powder added, and group 2 was pure cobalt-chromium alloy powder with 1% of unetched Ni-coated Al added2O3Composite powder, 1%, 2% and 3% Ni-coated Al is added into groups 3-52O3And (3) compounding the powder.
The mechanical properties and the friction resistance of the various groups of molded parts were tested, and the specific test values are shown in table 1.
As can be seen from Table 1, regardless of Ni-coated Al2O3Whether the composite powder is etched or not, the mechanical strength and the abrasion resistance of the cobalt-chromium alloy mixed with the composite powder are obviously superior to those of a workpiece prepared by pure cobalt-chromium alloy powder. Under the same mixing amount, Ni-coated Al is mixed2O3The mechanical strength and the friction resistance of the formed part of the cobalt-chromium alloy powder of the composite powder are superior to those of the formed part of the cobalt-chromium alloy powder mixed with the non-etched Ni coated Al2O3The cobalt chromium alloy powder of the composite powder is formed into a product.
Further, Al is coated with Ni2O3The mixing amount of the composite powder is increased, the mechanical strength and the friction resistance of a formed part of the cobalt-chromium alloy powder are improved, when the mixing amount of the composite powder is 2%, the abrasion resistance is best, and the abrasion rate is improved by nearly 61% compared with that of the cobalt-chromium alloy part without the composite powder.
Figure DEST_PATH_IMAGE001
Example 2.
And uniformly mixing 30ml of formic acid and 4ml of 30% hydrogen peroxide to obtain the etching solution.
Adding 1.5g ZrO into the etching solution2Magnetic stirring the powder for 60min, filtering, washing with deionized water for 3 times, washing with anhydrous ethanol for 2 times, and oven drying at 70 deg.C for 1h to obtain etched ZrO2And (3) powder.
0.5g of stannous chloride dihydrate is weighed and dissolved in 1ml of concentrated hydrochloric acid, and deionized water is used for fixing the volume to 50ml to obtain the sensitizing solution.
0.02g of palladium chloride is weighed, dissolved in 0.3ml of concentrated hydrochloric acid, and the volume is adjusted to 50ml by deionized water, so as to obtain the activation solution.
Etching ZrO2Placing the powder in sensitizing solution, magnetically stirring for 40min, centrifuging, washing with deionized water for 3 times, and washing with anhydrous ethanol for 2 times to obtain sensitized ZrO2And (3) powder.
Finally, the sensitized ZrO2Placing the powder in the containerMagnetically stirring the solution for 40min, centrifuging, washing with deionized water for 3 times, washing with anhydrous ethanol for 2 times, and oven drying at 70 deg.C for 1.5 hr to obtain activated ZrO2And (3) powder.
Weighing 1g of nickel sulfate hexahydrate, 1.5g of sodium citrate, 1g of boric acid and 1mg of PVP, adding into deionized water, stirring and dissolving, then adding 2ml of hydrazine hydrate, and fixing the volume to 50ml with the deionized water to prepare the chemical plating solution.
Adjusting the pH of the electroless plating solution to 12, adding the activated ZrO2Placing the powder in a cell crusher, and reacting for 1h at 60 ℃.
After the reaction is finished, standing and separating out a reaction product, washing for 3 times by using deionized water, washing for 2 times by using absolute ethyl alcohol, and freeze-drying until the drying is finished to obtain Ni-coated ZrO coated with uniform plating2And (3) compounding the powder.
Comparative example 2.
1.5g of ZrO were weighed2Powder, which was sensitized and activated without etching by the method of example 2, was placed in electroless plating solution to react and obtain non-etched Ni-coated ZrO2Composite powder, which served as a control.
Example 2 is applied.
Ni-coated ZrO prepared in example 22Composite powder and unetched Ni-coated ZrO prepared in comparative example 22The composite powder is mixed in cobalt-chromium alloy powder according to a certain proportion, and a selective laser melting forming process is adopted to prepare a cobalt-chromium alloy part with a specific shape on a stainless steel substrate.
The selective laser melting forming process and the application example 1 are used for experiments to set 5 groups in total, wherein no composite powder is added into the group 1, the composite powder is pure cobalt-chromium alloy powder, and 1% of non-etched Ni-coated ZrO is added into the group 22Composite powder, wherein 1%, 2% and 3% of Ni-coated ZrO are added into groups 3-5 respectively2And (3) compounding the powder.
The mechanical properties and the friction resistance of the various groups of molded parts prepared were tested, and the specific test values are shown in table 2.
As can be seen from Table 2, regardless of the Ni-coated ZrO2Whether the composite powder is etched or not, and the mechanical strength and the abrasion resistance of the cobalt-chromium alloy mixed with the composite powderAre all obviously superior to the finished parts prepared by pure cobalt-chromium alloy powder. At the same mixing amount, Ni-coated ZrO is mixed2The mechanical strength and the friction resistance of the cobalt-chromium alloy powder forming part of the composite powder are superior to those of the cobalt-chromium alloy powder forming part mixed with the non-etched Ni-coated ZrO2The cobalt chromium alloy powder of the composite powder is formed into a product.
In addition, ZrO coated with Ni2The increase of the mixing amount of the composite powder improves the mechanical strength and the friction resistance of a formed part of the cobalt-chromium alloy powder, when the mixing amount of the composite powder is 3 percent, the wear resistance is the best, and the wear rate is improved by nearly 57 percent compared with the cobalt-chromium alloy part without the composite powder.
Figure DEST_PATH_IMAGE002
Example 3.
40ml of formic acid and 4ml of 30% hydrogen peroxide are uniformly mixed to obtain the etching solution.
Adding 2.5g of SiC powder into the etching solution, magnetically stirring for 60min, filtering, washing with deionized water for 4 times, washing with absolute ethyl alcohol for 3 times, and drying in an oven at 80 ℃ for 0.5h to obtain the etched SiC powder.
Weighing 2g of stannous chloride dihydrate, dissolving the stannous chloride dihydrate in 3ml of concentrated hydrochloric acid, and fixing the volume to 50ml by using deionized water to obtain the sensitizing solution.
0.05g of palladium chloride is weighed, dissolved in 0.75ml of concentrated hydrochloric acid, and the volume is adjusted to 50ml by deionized water, so as to obtain the activation solution.
And (3) placing the etched SiC powder into a sensitizing solution, magnetically stirring for 50min, centrifugally separating, washing with deionized water for 4 times, and washing with absolute ethyl alcohol for 3 times to obtain the sensitized SiC powder.
And finally, placing the sensitized SiC powder in an activation solution, magnetically stirring for 50min, centrifugally separating, washing with deionized water for 4 times, washing with absolute ethyl alcohol for 3 times, and drying in an oven at the temperature of 80 ℃ for 0.5h to obtain the activated SiC powder.
Weighing 2g of nickel sulfate hexahydrate, 4.5g of sodium citrate, 2.5g of boric acid and 3mg of PVP, adding into deionized water, stirring and dissolving, adding 3ml of hydrazine hydrate, and fixing the volume to 50ml with the deionized water to prepare the chemical plating solution.
Adjusting the pH value of the chemical plating solution to 11, adding the activated SiC powder, placing the activated SiC powder in a cell crushing instrument, and reacting for 1.5h at 80 ℃.
And after the reaction is finished, standing to separate out a reaction product, washing with deionized water for 4 times, washing with absolute ethyl alcohol for 3 times, and freeze-drying until the drying is finished to obtain the uniformly plated Ni-coated SiC composite powder.
Comparative example 3.
2.5g of SiC powder was weighed, sensitized and activated directly according to the method of example 3 without etching, and placed in a chemical plating solution to react to obtain non-etched Ni-coated SiC composite powder as a control.
Example 3 is applied.
The Ni-coated SiC composite powder prepared in example 3 and the unetched Ni-coated SiC composite powder prepared in comparative example 3 were mixed in cobalt-chromium alloy powder in a certain ratio, and a cobalt-chromium alloy product of a specific morphology was prepared on a stainless steel substrate by a selective laser melting molding process.
The selective laser melting forming process is similar to application example 1, and 5 groups are set in an experiment, wherein no composite powder is added in group 1, the composite powder is pure cobalt-chromium alloy powder, 1% of unetched Ni-coated SiC composite powder is added in group 2, and 1%, 2% and 3% of Ni-coated SiC composite powder are added in groups 3-5 respectively.
The mechanical properties and the friction resistance of the various groups of molded parts were tested, and the specific test values are shown in table 3.
According to table 3, the mechanical strength and abrasion resistance of the blended composite powder cobalt chromium alloy were significantly better than those of the article prepared from the pure cobalt chromium alloy powder, regardless of whether the Ni-coated SiC composite powder was etched or not. Under the same mixing amount, the mechanical strength and the friction resistance of the formed part of the cobalt chromium alloy powder mixed with the Ni-coated SiC composite powder are better than those of the formed part of the cobalt chromium alloy powder mixed with the non-etched Ni-coated SiC composite powder.
In addition, with the increase of the mixing amount of the Ni-coated SiC composite powder, the mechanical strength and the friction resistance of a formed part of the cobalt-chromium alloy powder are improved, when the mixing amount of the composite powder is 3%, the wear resistance is the best, and the wear rate is improved by nearly 67% compared with a cobalt-chromium alloy part without the composite powder.
Figure DEST_PATH_IMAGE003

Claims (10)

1. A preparation method of nickel-coated ceramic composite powder based on selective laser melting molding comprises the following steps:
1) mixing formic acid and hydrogen peroxide in a volume ratio of (5-10) to 1 to obtain etching liquid, and adding ceramic powder to perform surface etching to obtain etched ceramic powder;
2) adding the etched ceramic powder into stannous chloride sensitizing solution, and carrying out sensitization treatment to obtain sensitized ceramic powder;
3) adding the sensitized ceramic powder into palladium chloride activating solution for activation treatment to obtain activated ceramic powder;
4) and placing the activated ceramic powder in chemical nickel plating solution with the pH value of 11-13, and reacting for 0.5-2 h at 40-80 ℃ to obtain the uniformly plated nickel-coated ceramic composite powder.
2. The method according to claim 1, wherein the ceramic powder is any one of alumina, zirconia, mullite, silicon carbide, and boron carbide.
3. The preparation method according to claim 1, wherein the etching, sensitizing and activating treatment time is 30-50 min, and stirring treatment is assisted in the treatment process.
4. The preparation method according to claim 1, wherein the sensitizing solution contains 10-40 g/l of stannous chloride, 20-60 ml/l of concentrated hydrochloric acid, and the balance of deionized water; the activating solution contains 0.1-1 g/l of palladium chloride, 5-15 ml/l of concentrated hydrochloric acid and the balance of deionized water.
5. The method according to claim 1, wherein the electroless nickel plating solution comprises: 10-40 g/l of nickel sulfate hexahydrate, 30-60 ml/l of hydrazine hydrate, 30-90 g/l of sodium citrate, 10-50 ml/l of boric acid, 10-100 mg/l of PVP and the balance of deionized water.
6. The preparation method of claim 1, wherein the chemical nickel plating process is assisted by ultrasonic pulverization.
7. The method of claim 1, wherein the ceramic powder after etching, sensitizing, activating and nickel plating is washed and dried.
8. The preparation method of claim 1, wherein the amount of the ceramic powder added in the etching solution is 30-60 g/l.
9. The method according to claim 1, wherein the amount of the ceramic powder added to the sensitizing solution and the activating solution is 10 to 50 g/l.
10. The method according to claim 7, wherein the nickel-coated ceramic composite powder is vacuum freeze-dried.
CN202010100683.3A 2020-02-19 2020-02-19 Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding Active CN111185594B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010100683.3A CN111185594B (en) 2020-02-19 2020-02-19 Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010100683.3A CN111185594B (en) 2020-02-19 2020-02-19 Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding

Publications (2)

Publication Number Publication Date
CN111185594A CN111185594A (en) 2020-05-22
CN111185594B true CN111185594B (en) 2022-06-21

Family

ID=70687561

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010100683.3A Active CN111185594B (en) 2020-02-19 2020-02-19 Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding

Country Status (1)

Country Link
CN (1) CN111185594B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112548096A (en) * 2020-12-14 2021-03-26 中北大学 Cobalt-coated ceramic composite powder and preparation method and application thereof
CN114478074B (en) * 2022-01-12 2023-04-28 中北大学 Hydroxyapatite grafted cobalt coated ceramic composite powder and preparation and application thereof
CN114850472B (en) * 2022-03-25 2023-06-30 昆明理工大学 Method for coating ceramic particles and preparation method of composite material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630751A (en) * 2015-02-05 2015-05-20 太原理工大学 Boron carbide particle surface nickel plating method
CN110461104A (en) * 2018-05-07 2019-11-15 惠州市鸿宇泰科技有限公司 A kind of wiring board roughening treatment agent

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3084746B2 (en) * 1990-11-20 2000-09-04 ぺんてる株式会社 Flake-shaped metal-coated powder and method for producing the same
CN1245353C (en) * 2001-04-19 2006-03-15 宁波凌日表面工程有限公司 Method for preparing nanometer metal ceramic composite powder
CN105195737B (en) * 2015-10-14 2017-07-18 东南大学 A kind of method of SiC particulate surface cladded with nickel
WO2017199833A1 (en) * 2016-05-17 2017-11-23 Dic株式会社 Electroless nickel plating method
CN106929835A (en) * 2017-03-02 2017-07-07 苏州金仓合金新材料有限公司 Chemical plating fluid and use its method to SiC particulate Surface coating Ni P
CN107675149A (en) * 2017-08-10 2018-02-09 安徽省凤形耐磨材料股份有限公司 A kind of method of ceramic grain surface nickel plating

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104630751A (en) * 2015-02-05 2015-05-20 太原理工大学 Boron carbide particle surface nickel plating method
CN110461104A (en) * 2018-05-07 2019-11-15 惠州市鸿宇泰科技有限公司 A kind of wiring board roughening treatment agent

Also Published As

Publication number Publication date
CN111185594A (en) 2020-05-22

Similar Documents

Publication Publication Date Title
CN111185594B (en) Preparation method of nickel-coated ceramic composite powder based on selective laser melting molding
CN106902390A (en) A kind of titanium alloy is implanted into composite material and its preparation and application
Ouyang et al. Powder metallurgical Ti-Mg metal-metal composites facilitate osteoconduction and osseointegration for orthopedic application
CN106902391A (en) A kind of magnesium alloy is implanted into composite material and its preparation and application
WO2017035893A1 (en) Polyetheretherketone/nano-hydroxyapatite composite material for sls technology and preparation method thereof
US20110195378A1 (en) Composite Bio-Ceramic Dental Implant and Fabricating Method Thereof
CN105169471A (en) Implant porous niobium-titanium alloy material for medical use and preparation method of alloy material
CN105274603A (en) Compound modified coating of magnesium or magnesium alloy surface carbon-containing nano tube and preparation method of compound modified coating
CN112500150A (en) Magnesium alloy/biological ceramic porous scaffold and preparation method and application thereof
CN108543109B (en) Low-abrasion dual-antibacterial titanium-based nanocomposite bone implant and forming method thereof
CN106421907A (en) Preparation method of graphene oxide-based hybrid biological functional coating
CN106267342A (en) A kind of dentistry implant and preparation method thereof
CN110037813B (en) Titanium-based zirconia composite medical implant and 3D printing preparation method thereof
CN107475564A (en) A kind of preparation method of high-strength compact titanium alloy ceramics Biocomposite material
Kang et al. Advanced composite material: effect of composite SiC on compressive strength and hardness of porous titanium
CN112274301B (en) Ankle joint prosthesis system containing zirconium-niobium alloy with oxide layer and preparation method
CN112899752A (en) Method for preparing MAO-LDH coating with corrosion resistance and antibacterial property on surface of medical magnesium alloy and application
CN115414526B (en) Biodegradable zinc alloy bearing bone bracket with bionic structure and processing method
CN107137772B (en) Preparation method of carbon nano tube reinforced hydroxyapatite composite material
CN112620626B (en) Forming method of bone induction type titanium alloy bone implant with high antibacterial property
WO2022198965A1 (en) Titanium-molybdenum-based hydroxyapatite composite material for bone repair, and preparation method therefor
CN111206243B (en) Biomedical high-entropy alloy coating and preparation method thereof
CN112063886B (en) Magnesium-containing biological beta titanium alloy with micro/nano pores and preparation method thereof
CN114932225B (en) Medical 3D printing nickel-titanium-based composite powder, preparation method and composite reinforced material
Saba et al. Fabrication, mechanical property and in vitro bioactivity of hierarchical macro-/micro-/nano-porous titanium and titanium molybdenum alloys

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant