CN112091222A - Application of phenolic resin coating treatment process in preparation of powder metallurgy material by ball milling method - Google Patents
Application of phenolic resin coating treatment process in preparation of powder metallurgy material by ball milling method Download PDFInfo
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention relates to application of a phenolic resin coating treatment process in preparation of a powder metallurgy material by a ball milling method, belonging to the technical field of powder. The invention successfully solves the problem of difficult pressing-sintering caused by the processing and hardening of a matrix in the ball milling process by introducing the phenolic resin as a control agent for controlling the strength of the powder metallurgy material and dispersing agents of various added substances, simultaneously solves the problems of difficult uniform dispersion and obvious damage to the integrity of the added substance structure of various added substances in the crushing process, and ensures that the strength of the material is maintained in the subsequent high-temperature use process. Aiming at the hardness difference of soft and hard materials, in order to realize the dispersion of the substances with larger difference in hardness in metal, the invention utilizes different phenolic resin coating treatments, thereby reducing the influence of obvious work hardening caused by the ball milling of a matrix on the subsequent pressing-sintering while realizing uniform dispersion. The invention has simple preparation process and low cost, and is convenient for large-scale industrial application.
Description
Technical Field
The invention relates to an application of a phenolic resin coating treatment process in preparing a powder metallurgy material by a ball milling method; belonging to the technical field of powder processing hardening and particle or fiber dispersion control.
Background
The particle or fiber reinforced metal matrix composite material has the characteristics of high electrical and thermal conductivity, good toughness and corrosion resistance of metal, high strength, high toughness, high temperature resistance or wear resistance of particles or fibers and the like, and can be widely used as candidate materials in the fields of heat conduction materials, conductive materials, friction materials, structural materials and the like. Such materials are usually prepared by powder metallurgy, and in order to achieve excellent properties of the material, it is necessary to ensure uniform dispersion of the particulate or fibrous phase in the matrix metal as reinforcing and toughening.
In order to realize the dispersion of the reinforcing and toughening phase in the matrix metal, researchers have made a lot of researches, mainly focusing on adding a nonaqueous liquid phase medium (polymer solution) for dispersion, plating metal on the surfaces of particles or fibers, adding other alloy elements into the metal to reduce the wettability of the interface between the metal and the reinforcing phase and the matrix metal, and the like. The mechanical ball milling method is one of the important methods for obtaining the uniform dispersion of the reinforcing and toughening phase in the metal, but the ball milling process effectively disperses the reinforcing or toughening phase and simultaneously leads the processing and hardening of the matrix metal to be obvious, particularly when metal or ceramic particles with the Mohs hardness higher than 2 are ball milled, the hardening of the matrix metal is obvious along with the extension of the ball milling time, so that the stress concentration in the pressing process is obvious, the material is easy to crack due to the extremely large internal stress during sintering, the density is greatly reduced, and the dense sintering can be realized only by adopting a special powder metallurgy sintering process (such as hot isostatic pressing, discharge plasma sintering, self-propagating sintering and the like), thereby limiting the industrial production of the material.
Chinese invention patent CN104388847B discloses a preparation method of a carbon fiber reinforced copper-based composite material, which comprises the following steps: step one, weighing the ingredients, and performing ball milling and mixing for 3 hours; obtaining a mixture; the surface of the carbon fiber is coated with a nickel layer; the particle size of the graphite powder is 50 μm, and the surface of the graphite powder is plated with a copper layer by chemical plating technology; step two, pressing the mixture prepared in the step one under the pressure of 700 MPa; obtaining a blank; step three, performing secondary sintering on the blank prepared in the step two to obtain a sintered alloy block; step four, carrying out heat treatment on the alloy block treated in the step three; the carbon fiber reinforced copper-based composite material is obtained. The copper-based composite material prepared by the invention not only has excellent self-lubricating property, but also has excellent wear resistance and mechanical property. However, the carbon fibers and the nickel powder, the iron powder and the copper powder are mixed by ball milling, so that the carbon fibers are seriously damaged, and meanwhile, the carbon fibers are unevenly distributed and the carbon fibers and the copper are obviously incompatible at interfaces due to the adoption of the pressing and high-temperature sintering method for preparing the material, so that the performance of the material is further influenced.
The Chinese patent CN108441791A discloses a carbon fiber reinforced metal ceramic composite material, which consists of a carbon fiber preform, an interface layer, a ceramic matrix and a metal matrix, wherein the metal is one of aluminum alloy, magnesium alloy, copper alloy and tin alloy, the ceramic is SiC, and the density of the composite material is 1.8-3.8 g/cm3The patent also discloses a method for preparing different alloy ceramic composite materials. The composite material has the advantages of short preparation period and adjustable density, overcomes the brittleness and low density of ceramics, and can meet the requirements of various fields on the ceramic matrix composite material. However, in the invention, the ceramic matrix is prepared in the carbon fiber preform firstly, and then the metal matrix is prepared, so that although the carbon fiber is protected from being damaged by molten metal, the carbon fiber is inevitably damaged by preparing the ceramic matrix in the carbon fiber preform with the interface layer by a precursor impregnation cracking method, and the generated ceramic interface layer is high in brittleness and has adverse effect on performance.
The inventor researches and discovers that the phenolic resin coated carbon fiber and the soft metal are subjected to ball milling to obtain metal powder in which carbon particles or short carbon fibers are uniformly embedded. The Chinese invention patent CN108018506A discloses a short carbon fiber modified high-friction composite material, which comprises the following raw materials: 1-3 wt.% of short carbon fiber is coated and cured by resin; the dispersion strengthening copper powder of the nano oxide is more than or equal to 15wt percent; in the nano-oxide dispersion strengthened copper powder, the nano-oxide is generated in situ. The short carbon fiber and the copper powder are subjected to resin coating-curing treatment and ball milling to prepare pre-alloyed powder, and then the pre-alloyed powder is mixed with other component powder and is pressed and sintered to prepare the short carbon fiber modified high-friction composite material. In this patent, a carbonization treatment is carried out on the coated phenolic resin; carrying out high-energy ball milling after carbonization; although the carbonization treatment can effectively shorten the length of the short carbon fiber, the carbonized phenolic resin coating layer is too brittle, the protection effect on the carbon fiber structure is weakened, the deformation of the copper powder is aggravated in the ball milling process, and the subsequent heat treatment annealing process is combined to improve the plasticity of the copper powder so as to improve the pressing performance of the copper powder. Therefore, the control of the carbonization process of the carbon fiber coated by the phenolic resin not only has important influence on the structural integrity of the carbon fiber and the pressing performance of the metal powder, but also causes the carbon fiber to be obviously crushed due to improper control, the copper powder is obviously hardened, the plasticity of the carbon fiber cannot be effectively improved even through subsequent annealing treatment, and the cost of the process is increased due to the vacuum carbonization treatment at 800-1200 ℃.
Aiming at the hardness difference of soft and hard materials, in order to realize the dispersion of the reinforcing or toughening phases with larger difference in hardness in metal, different phenolic resin coating-curing treatments are utilized to replace phenolic resin coating-carbonizing treatments, and a mechanical ball milling process is combined, so that the influence of obvious work hardening caused by the ball milling of matrix metal on subsequent pressing-sintering is reduced while uniform dispersion is realized, the preparation process is simple, and the cost is low.
Disclosure of Invention
In order to solve the technical defect of poor sintering compactness caused by uniform dispersion of soft and hard reinforcing or toughening phases in metal and remarkable processing and hardening of matrix metal in the existing mechanical ball milling process, the invention provides application of a phenolic resin coating treatment process in preparing a powder metallurgy material by a ball milling method, and aims to prepare a particle-reinforced or fiber-toughened metal-based composite material (the composite material is also called as a composite material for short) with good compactness and excellent strength, toughness and other properties.
The metal-based composite material can be reinforced or toughened by adopting metal or ceramic particles or fibers, the mechanical ball milling process is one of the simplest processes for realizing the dispersion of the substances, but the hard phase can cause the hardening of matrix metal to be obvious while the ball milling dispersion is carried out, so that the pressing, sintering and forming are difficult. The wear-resisting property of the metal-based composite material can be obviously improved by adopting soft materials such as graphite, but the structure of the graphite can be obviously damaged by the ball milling process, so that the graphite is obviously crushed, and the performance of the graphite is not favorably exerted.
Through intensive research, the inventor firstly proposes that different phenolic resin curing processes are selected for soft and hard reinforcing or toughening phases, so as to obtain phenolic resin coating layers of the reinforcing or toughening phases with different hardness degrees, and the soft phenolic resin coating layers are utilized to absorb energy in the ball milling process of the hard reinforcing or toughening phases, so that the processing hardening of matrix metal is greatly reduced; the hard phenolic resin coating layer is utilized to protect the damage of the structure, the shape and the granularity in the ball milling process of the soft reinforcing or toughening phase, and the densification of the material under the traditional pressing-sintering condition is realized while the uniform dispersion of the reinforcing or toughening phase is ensured. The method comprises the following specific steps:
the application of the phenolic resin coating treatment process in the preparation of the powder metallurgy material by the ball milling method is characterized in that the phenolic resin coating treatment process is applied to a control agent for preparing the powder metallurgy material by the ball milling method, wherein the control agent has high strength and low strength; dipping the reinforcing or toughening phase in an organic solution containing phenolic resin, drying to obtain a reinforcing and/or toughening phase coated by the phenolic resin, then ball-milling the reinforcing and/or toughening phase and matrix metal powder until the reinforcing and/or toughening phase is uniformly mixed and a phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the range of variation in hardness of the matrix metal powder after ball milling-the hardness of the matrix metal powder before ball milling is 10% or less.
The invention relates to an application of a phenolic resin coating treatment process in preparing powder metallurgy materials by a ball milling method, wherein a reinforcing phase is at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials;
the toughening phase is at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials.
The invention relates to an application of a phenolic resin coating treatment process in preparing powder metallurgy materials by a ball milling method,
the reinforcing phase and/or toughening phase is one or more of particles, fibers and particles after the fibers are crushed and is mixed according to any proportion.
When the Mohs hardness of a reinforcing or toughening phase is not lower than 2, placing the reinforcing and/or toughening phase in an organic solution containing phenolic resin at the temperature of 60-80 ℃, soaking for 1-2 hours, and drying for 1-3 hours at the low temperature (80-100 ℃) to obtain the reinforcing and/or toughening phase coated with the phenolic resin; then ball milling with matrix metal powder until the mixture is uniformly mixed and the phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the range of variation in hardness of the matrix metal powder after ball milling-the hardness of the matrix metal powder before ball milling is 10% or less.
When the Mohs hardness of a reinforcing or toughening phase is less than or equal to 2, placing the reinforcing and/or toughening phase in an organic solution containing phenolic resin at the temperature of 60-80 ℃, soaking for 1-2 h, and drying for 1-3 h at low temperature (180-200 ℃) to obtain a reinforcing phase and/or toughening phase coated with the phenolic resin; then ball milling with matrix metal powder until the mixture is uniformly mixed and the phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the range of variation in hardness of the matrix metal powder after ball milling-the hardness of the matrix metal powder before ball milling is 10% or less.
The invention relates to application of a phenolic resin coating treatment process in preparation of powder metallurgy materials by a ball milling method, wherein an organic solution containing phenolic resin is a phenolic resin alcohol saturated solution.
The invention relates to application of a phenolic resin coating treatment process in preparation of powder metallurgy materials by a ball milling method, wherein a matrix metal is at least one selected from silver, aluminum, copper, titanium, iron, manganese, cobalt, nickel and chromium. As a preference; the base metal is at least one of aluminum, copper, titanium, iron and nickel.
The application of the phenolic resin coating treatment process in the preparation of the powder metallurgy material by the ball milling method is characterized in that the rotating speed of the ball milling is 150-300 r/min.
The specific application method comprises the steps of placing a ceramic material A, a metal material A and the like with Mohs hardness not lower than 2 in a phenolic resin alcohol saturated solution at the temperature of 60-80 ℃, soaking for 1-2 hours, drying at the low temperature (80-100 ℃) for 1-3 hours, or placing a graphite material B and the like with Mohs hardness lower than 2 in a phenolic resin alcohol saturated solution at the temperature of 60-80 ℃, soaking for 1-2 hours, and drying at the high temperature (180-200 ℃) for 5-30 minutes to obtain a phenolic resin coated material A or B. Then ball milling with the base metal C to obtain the powder A or B which is uniformly dispersed or uniformly embedded in the metal C.
The principle and the advantages of the invention are as follows:
the mechanical ball milling process is an effective and simplest method for obtaining a uniformly mixed material, and is particularly effective for the controllable addition of a reinforcing phase or a toughening phase. But the requirements of the ball mill on the raw materials, as well as the extent of work hardening of the base metal, have a significant impact. First, as for the reinforcing phase particles, the kind of particles determines the degree of dispersion in the metal, and soft particle phases such as graphite are easily and rapidly broken during ball milling and are crushed before being dispersed, so that the structural damage is extremely serious. The hard particle phase (e.g., ceramic particles) is relatively easily dispersed in the matrix metal powder, but while dispersed, the hard particles work harden significantly relative to the matrix metal powder, resulting in difficult forming during pressing and less dense sintering, and significant internal stress in the material causes significant cracking of the material. For the toughening phase fiber, most of the fibers have higher flexibility, especially carbon fibers, carbon nanotubes and the like, and are very easy to wind in the ball milling process, so that the uniform dispersion cannot be realized or is difficult to realize. And part of hard fibers, such as SiC fibers, glass fibers and the like, are quickly damaged in the ball milling process, and obviously harden the matrix metal.
In order to realize the uniform dispersion of the reinforcing phase and the toughening phase and reduce the influence on the processing and hardening of the matrix metal powder, different phenolic resin curing processes are firstly proposed to obtain phenolic resin coating layers of the reinforcing or toughening phase with different hardness degrees, and the soft phenolic resin coating layers are utilized to absorb the energy in the ball milling process of the hard reinforcing or toughening phase, so that the processing and hardening of the matrix metal are greatly reduced; the hard phenolic resin coating layer is utilized to protect the damage of the structure, the shape and the granularity in the ball milling process of the soft reinforcing or toughening phase, and the required fiber length can be obtained by mechanical ball milling time aiming at the material which needs to have the length requirement on the fiber of the toughening phase. The method ensures that the reinforcing or toughening phase is uniformly dispersed, and simultaneously realizes the densification of the material under the traditional pressing-sintering condition.
The preparation process is simple, the cost is low, and the preparation of the metal-based composite material which takes the metal powder with dispersed or embedded reinforcing phase or toughening phase as the raw material and mainly adopts the ball milling process is realized only by regulating and controlling the resin coating layer.
The composite material prepared by directly taking reinforcing phase particles or toughening phase fibers and the like as raw materials and carrying out ball milling with matrix metal powder without any treatment is shown in figures 1, 3 and 5. As can be seen from fig. 1, when the added particles are soft graphite, the graphite is rapidly broken and agglomerated during the ball milling process, and the dispersion cannot be achieved. As can be seen from FIG. 5, the reinforcing phase particles are hard ZrO2When the ball milling is carried out, the deformation of the matrix metal powder is obvious in the ball milling process. As is clear from fig. 3, when the toughening phase is a SiC whisker having high hardness and brittleness, the SiC whisker is broken and agglomerated after ball milling, and thus dispersion cannot be achieved. As can be seen from FIG. 6, even for hard reinforcing phase ZrO2If the particles are coated with a phenolic resin, if the coating is not selected properly, the particles are cured to form a hard carbon layer, which can relieve the work hardening of the reinforcing phase particles to the metal powder to some extent, but still cannot solve the problem.
As can be seen from fig. 2, 4 and 7, after the appropriate phenolic resin coating treatment process is adopted, uniform dispersion of particles or fibers and the like is realized, and meanwhile, the work hardening of the powder is obviously reduced, so that the subsequent pressing and sintering are facilitated, and the method has a good market prospect.
Drawings
FIG. 1 shows SEM morphology of crushed and agglomerated carbon powder obtained by directly ball-milling graphite and copper powder in comparative example 1;
FIG. 2 is an SEM image of mixed powder obtained in example 1 by coating graphite with a phenolic resin and ball-milling the graphite and copper powder;
FIG. 3 is an SEM appearance of SiC whiskers which are crushed and agglomerated after SiC whiskers and copper powder are directly ball-milled in a comparative example 2;
FIG. 4 is an SEM image of mixed powder obtained by pre-coating SiC whiskers with a phenolic resin and ball-milling the SiC whiskers and copper powder in example 2;
FIG. 5 shows ZrO prepared by directly mixing ZrO in comparative example 32After the particles and the nickel powder are ball-milled, the SiC crystal whiskers are crushed and agglomerated and have SEM appearance;
FIG. 6 shows ZrO in advance in comparative example 42Carrying out phenolic resin coating treatment on the particles to obtain a coating layer which is a hard phenolic resin layer, and carrying out SEM appearance on mixed powder subjected to ball milling with nickel powder;
FIG. 7 shows ZrO in advance in example 32And after the particles are coated with phenolic resin, the obtained coating layer is a soft phenolic resin layer, and the SEM appearance of the mixed powder is obtained after the particles are ball-milled with nickel powder.
As can be seen from FIG. 1, the crystalline flake graphite is not coated with phenolic resin, but is directly ball-milled with electrolytic copper powder, and after ball milling, the graphite is broken obviously and is agglomerated.
As can be seen from fig. 2, the graphite is coated with the phenolic resin in advance, and then ball-milled with the copper powder, which shows that the hard phenolic resin coating layer can effectively protect the graphite from being damaged in shape and structure, and has little influence on the electrolytic copper powder.
As can be seen from fig. 3, the SiC whiskers were not coated with the phenolic resin, but were ball-milled with copper powder, and the broken SiC whiskers were broken and agglomerated significantly.
As can be seen from fig. 4, the SiC whiskers were coated with a phenol resin in advance and then ball-milled with copper powder, and it was found that the soft phenol resin coating layer can effectively protect the shapes of the SiC whiskers, shorten the length of the SiC whiskers, and have little influence on electrolytic copper powder while achieving whisker dispersion.
As can be seen from FIG. 5, ZrO was subjected to annealing2The particles are not coated with phenolic resin, and are directly ball-milled with electrolytic nickel powder, and the nickel powder is changed into a flat large-particle shape from a dendritic shape.
As can be seen from FIG. 6, ZrO was previously mixed2The particles are coated with phenolic resin to obtain a coating layer of hard phenolic resinAnd ball milling the layer with electrolytic nickel powder to change the nickel powder from dendritic state to large particle spherical state. It is shown that the hard phenolic resin coating layer does not alleviate the work hardening of the base metal, resulting in significant deformation of the metal powder.
As can be seen from FIG. 7, ZrO was previously formed2After the particles are coated with phenolic resin, the particles are ball-milled with electrolytic nickel powder, ZrO2The particles are embedded into the nickel powder particles, the morphology of the nickel powder is not obviously changed, and the soft phenolic resin coating layer can realize ZrO2The particles are uniformly embedded without causing significant work hardening of the base metal powder.
Detailed Description
The technical solutions of the present invention are clearly and completely described below with reference to the drawings of the present invention, and it is obvious that the described embodiments are only some of the technical solutions described in the present invention, but not all of the technical solutions described in the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Comparative example 1
The comparative example 1 was conducted under the same conditions as in example 1 except that the crystalline flake graphite was directly ball-milled with electrolytic copper powder (having a hardness of 38HV) without being coated with a phenolic resin, and the ball-milling process was conducted in the same manner as in example 1. After ball milling, the graphite is broken obviously, and agglomeration occurs, and the SEM appearance of the agglomerated graphite particles is shown in figure 1. The hardness of the copper powder after ball milling was 41 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 400MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered at 920 ℃ for 2h, and the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, so that the room-temperature hardness of the sample of the comparative example 1 is 66HV, the 300-DEG C hardness is 42HV, and the 400-DEG C hardness is 36 HV.
Comparative example 2
The other conditions of the comparative example 2 are the same as those of the example 1, except that the crystalline flake graphite is subjected to phenolic resin coating treatment, then is subjected to vacuum carbonization treatment at 900 ℃ for 0.5h, and finally is ball-milled with electrolytic copper powder (the hardness of the electrolytic copper powder is 38HV), and the ball-milling process is the same as that of the example 1. After ball milling, the graphite is obviously crushed, and agglomeration phenomenon also occurs, and the morphology of the agglomerated graphite particles is similar to that of the figure 1. The hardness of the copper powder after ball milling was 44 Hv. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 400MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 920 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the hardness of the sample piece in the comparative example 2 is 68HV, the hardness at 300 ℃ is 41HV, and the hardness at 400 ℃ is 37 HV.
Example 1
In this example 1, crystalline flake graphite coated with phenolic resin and electrolytic copper powder are added into a ball mill for high-energy ball milling. The grain size of the selected electrolytic copper powder is 150 microns (the hardness is 38HV), and the grain size of the flake graphite is 100 microns. Dissolving the prepared phenolic resin in an organic solvent to obtain a phenolic resin alcohol saturated solution, then soaking the crystalline flake graphite in the phenolic resin alcohol saturated solution at 80 ℃ for 2h, and drying at 200 ℃ for 10 min. And then ball-milling the graphite powder with electrolytic copper powder, wherein the volume ratio of the electrolytic copper powder to the crystalline flake graphite is 5: 1, ball milling rotation speed is 200 r/min, ball milling time is 0.5h, ball milling balls are stainless steel balls, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the weight of the flake graphite and the electrolytic copper powder to the ball milling balls is 1: 6. The SEM morphology of the mixed powder of graphite and copper powder after ball milling is shown in FIG. 2. The hardness of the copper powder after ball milling was 39 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 400MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 920 ℃, and the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, so that the hardness of the sample in the embodiment 1 is 70HV, the hardness at 300 ℃ is 71HV, and the hardness at 400 ℃ is 76 HV.
Comparative example 3
The comparative example 3 was conducted under the same conditions as in example 2 except that the SiC whiskers were directly ball-milled with electrolytic copper powder (having a hardness of 38HV) without being coated with a phenolic resin, and the ball-milling process was conducted in the same manner as in example 2. After ball milling, the SiC whiskers are broken obviously, and the SEM appearance of the agglomerated SiC whiskers is shown in figure 3. The hardness of the copper powder after ball milling was 45 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 400MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 920 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the hardness of the sample piece in the comparative example 3 is 65HV, the hardness at 300 ℃ is 39HV, and the hardness at 400 ℃ is 34 HV.
Example 2
In this example 2, the SiC whiskers coated with the phenolic resin and the electrolytic copper powder were added to a ball mill for high-energy ball milling. The grain size of the selected electrolytic copper powder was 150 μm (the hardness was 38HV), and the SiC whiskers were 2 μm in diameter and 200 μm in length. Dissolving the prepared phenolic resin in an organic solvent to obtain a phenolic resin alcohol saturated solution, then soaking the SiC whiskers in the phenolic resin alcohol saturated solution at 80 ℃ for 2h, and drying at 100 ℃ for 2 h. Then ball-milling the SiC crystal whisker with electrolytic copper powder, wherein the volume ratio of the electrolytic copper powder to the SiC crystal whisker is 8:1, ball milling rotation speed is 220 r/min, ball milling time is 1h, the ball milling ball is a stainless steel ball, the ball diameter is 3 mm-10 mm (the mass ratio of the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm and 9mm is 4:8:11:20:12:8:6:1), and the mass ratio of the sum of the SiC crystal whisker and the electrolytic copper powder to the ball milling ball is 1: 6. The SEM appearance of the mixed powder of SiC whiskers and copper powder after ball milling is shown in FIG. 4. The hardness of the copper powder after ball milling was 48.5 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 400MPa, the pressure maintaining time is 20s, the prepared copper-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 920 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the hardness of the sample piece in the embodiment 2 is 69HV, the hardness at 300 ℃ is 71HV, and the hardness at 400 ℃ is 75 HV.
Comparative example 4
Comparative example 3 other conditions were the same as in example 3 except that ZrO was used2The particles were directly ball-milled with electrolytic nickel powder (nickel powder hardness: 50HV) without being coated with phenol resin, and the ball-milling process was the same as in example 3. After ball milling, the nickel powder is obviously deformed and changed into large flat particles from dendritic shapes, and the SEM appearance of the nickel powder is shown in FIG. 5.The hardness of the nickel powder after ball milling was 65 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared nickel-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 1000 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the hardness of the sample of comparative example 4 is 110HV, the hardness at 400 ℃ is 82HV, and the hardness at 600 ℃ is 68 HV.
Comparative example 5
Comparative example 5 other conditions were the same as in example 3 except that ZrO was used2The phenolic resin coating treatment process of the particles comprises the following steps: dissolving the prepared phenolic resin in an organic solvent to obtain a phenolic resin alcohol saturated solution, and then, dissolving ZrO in the alcohol saturated solution2The particles are soaked in 80 ℃ phenolic resin alcohol saturated solution for 2h and then dried for 30min at 900 ℃. And then ball-milled with electrolytic nickel powder (the nickel powder has a hardness of 50HV), the ball-milling process being the same as in example 3. After ball milling, the nickel powder still deforms obviously, changes from dendritic shape to spherical shape of large particles, and the SEM appearance is shown in FIG. 6. The hardness of the nickel powder after ball milling was 68 HV. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared nickel-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 1000 ℃, the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, and the hardness of the sample piece of the comparative example 5 is 115HV, the hardness at 400 ℃ is 80HV, and the hardness at 600 ℃ is 67 HV.
Example 3
EXAMPLE 3 ZrO coated with phenolic resin2The particles and the electrolytic nickel powder are added into ball milling equipment for high-energy ball milling. The particle size of the selected electrolytic nickel powder is 100 μm (the hardness of the nickel powder is 50HV), ZrO2The particle size of the particles was 5 μm. Dissolving the prepared phenolic resin in an organic solvent to obtain a phenolic resin alcohol saturated solution, and then, dissolving ZrO in the alcohol saturated solution2The particles are soaked in 80 ℃ phenolic resin alcohol saturated solution for 2h and then dried for 2h at 100 ℃. Then ball-milling with electrolytic nickel powder, the electrolytic nickel powder and ZrO2The volume ratio of the particles is 10: 1, the ball milling speed is 220 r/min, the ball milling time is 1h, the ball milling balls are stainless steel balls, the ball diameter is 3 mm-10 mm (the ball milling ball diameter is 3mm, 4mm, 5mm, 6mm, 7mm, 8mm,9mm in a mass ratio of 4:8:11:20:12:8:6:1), ZrO 22The mass ratio of the sum of the mass of the particles and the electrolytic nickel powder to the ball grinding ball is 1: 6. ZrO after ball milling2The SEM morphology of the mixed powder of particles and nickel powder is shown in fig. 7. The hardness of the nickel powder after ball milling was 52 Hv. And then cold pressing the mixed powder at room temperature, wherein the pressing pressure is 450MPa, the pressure maintaining time is 20s, the prepared nickel-based composite material pressed blank is subjected to pressure sintering under the protection of hydrogen atmosphere, the pressed blank is sintered for 2h at 1000 ℃, and the heating rate and the cooling rate of a furnace are both 10-15 ℃/min, so that the hardness of the sample of the comparative example 5 is 118HV, the hardness at 400 ℃ is 119HV, and the hardness at 600 ℃ is 110 HV.
Claims (8)
1. The application of the phenolic resin coating treatment process in preparing powder metallurgy materials by a ball milling method is characterized in that: applying a phenolic resin coating treatment process to a ball milling method to prepare a control agent for controlling the strength of the powder metallurgy material; dipping the reinforcing or toughening phase in an organic solution containing phenolic resin, drying to obtain a reinforcing and/or toughening phase coated by the phenolic resin, then ball-milling the reinforcing and/or toughening phase and matrix metal powder until the reinforcing and/or toughening phase is uniformly mixed and a phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the hardness of the base metal powder after ball milling-the range of variation of the base metal powder before ball milling is less than or equal to 10%.
2. The use of the phenolic resin coating process of claim 1 in the preparation of powder metallurgy materials by a ball milling process, wherein:
the reinforcing phase is at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials;
the toughening phase is at least one of zero-dimensional, one-dimensional, two-dimensional and three-dimensional materials.
3. The use of the phenolic resin coating process of claim 1 in the preparation of powder metallurgy materials by a ball milling process, wherein:
the reinforcing phase and/or toughening phase is one or more of particles, fibers and particles after the fibers are crushed and is mixed according to any proportion.
4. The use of the phenolic resin coating process of claim 2 in the preparation of powder metallurgy materials by a ball milling process, wherein: when the Mohs hardness of the reinforcing or toughening phase is not lower than 2, placing the reinforcing and/or toughening phase in an organic solution containing phenolic resin at the temperature of 60-80 ℃, soaking for 1-2 h, and drying for 1-3 h at low temperature (80-100 ℃) to obtain a reinforcing phase and/or toughening phase coated by the phenolic resin; then ball milling with matrix metal powder until the mixture is uniformly mixed and the phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the range of variation in hardness of the matrix metal powder after ball milling-the hardness of the matrix metal powder before ball milling is 10% or less.
5. The use of the phenolic resin coating process of claim 2 in the preparation of powder metallurgy materials by a ball milling process, wherein: when the Mohs hardness of the reinforcing or toughening phase is less than or equal to 2, placing the reinforcing and/or toughening phase in an organic solution containing phenolic resin at the temperature of 60-80 ℃, soaking for 1-2 h, and drying for 1-3 h at low temperature (180-200 ℃) to obtain a reinforcing phase and/or toughening phase coated by the phenolic resin; then ball milling with matrix metal powder until the mixture is uniformly mixed and the phenolic resin coating layer coated by the reinforcing and/or toughening phase cracks or falls off;
obtaining metal powder with uniformly dispersed or uniformly embedded reinforcing or toughening phases;
the range of variation in hardness of the matrix metal powder after ball milling-the hardness of the matrix metal powder before ball milling is 10% or less.
6. The use of the phenolic resin coating process of claim 1 in the preparation of powder metallurgy materials by a ball milling process, wherein: the organic solution containing the phenolic resin is a phenolic resin alcohol saturated solution.
7. The use of the phenolic resin coating process of claim 1 in the preparation of powder metallurgy materials by a ball milling process, wherein: the matrix metal is at least one selected from silver, aluminum, copper, titanium, iron, manganese, cobalt, nickel and chromium.
8. The use of the phenolic resin coating process of claim 1 in the preparation of powder metallurgy materials by a ball milling process, wherein: the rotation speed of the ball milling is 150-300 r/min.
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