CN113172365A - Preparation method of ternary boride hard alloy surfacing welding electrode - Google Patents
Preparation method of ternary boride hard alloy surfacing welding electrode Download PDFInfo
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Abstract
The invention discloses a preparation method of a ternary boride hard alloy surfacing electrode, belonging to the technical field of electrodes, and comprising S1, raw material treatment; s2, preparing an adhesive; s3, mixing materials; s4, preparation; and S5, sintering. According to the invention, a wax-based binder with low melting point and good fluidity is selected, different alloy element mass fractions are selected from the ternary boride raw material alloy powder to control the final sintering temperature, the target sintering temperature is reached through the integration of degreasing and sintering and the multi-stage heating program, the heating rate and the heat preservation time are controlled, the defects of deformation, cracks and the like of a welding rod blank in the heating and sintering processes can be effectively avoided, the diameter and the length of the ternary boride hard alloy surfacing welding rod can be flexibly adjusted, the ternary boride surfacing welding rod prepared by the method has uniform structure and components, the prepared coating has excellent performance, the dilution rate of the base metal is low, the quality of the coating is stable, the preparation cost is low, and the operation is simple.
Description
Technical Field
The invention belongs to the technical field of welding rods, and particularly relates to a preparation method of a ternary boride hard alloy surfacing welding rod.
Background
With the continuous development of the industry, higher requirements are put on the long-term effective stable work of mechanical parts, the performance of materials determines the service life of the parts, thus higher requirements are put on the performance of the materials, and the failure modes of the parts caused by the performance of the materials are mainly represented by surface failures, namely the surface abrasion and corrosion of the materials. Therefore, the effective improvement of the wear resistance and corrosion resistance of parts becomes a focus, and the coating technology for improving the surface performance of the material mainly comprises a brazing technology, an induction cladding technology, a laser cladding technology, a plasma cladding technology, a thermal spraying technology, a surfacing welding technology and the like, wherein the coating material and the coating process are key factors influencing the production efficiency, the cost, the coating quality and the performance.
Among a plurality of materials for improving the service life of parts, the ternary boride hard alloy becomes a research hotspot for improving the performance of the parts at present due to a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, and the flux-cored wire prepared by taking the ternary boride as a raw material is better applied to the field of material surface modification. However, the traditional flux-cored surfacing welding wire is a cylindrical welding rod prepared by wrapping flux cores (mainly metal powder) by a steel strip, but because the internal space of the steel strip is limited, the bird nest-like structure is formed among particles due to the uneven particle size of the powder, the prepared ternary boride hard alloy has uneven coating components, concentrated stress, cracked cladding and poor reliability, and because of the rapid heating and rapid cooling characteristics in the surfacing process, the powder material in the flux-cored welding wire does not have sufficient time to form the ternary boride in situ, so that the performance of the surfacing layer is not improved Sufficient formation of ternary boride hard phase and reduction of defects).
The single-screw extrusion molding mode is used as one of the traditional preparation modes of plastic bars and pipes such as PB, PE and the like, the molding quality is high, and continuous production can be realized, so that the preparation of the welding rod for ternary boride hard alloy surfacing by combining the powder metallurgy and the single-screw extrusion molding mode has high industrial value and wide application prospect.
Patent CN109623195A discloses a cermet flux-cored wire for heat-resistant and wear-resistant surfacing, which adds a composite reinforcing material (a mixture of zirconia and aluminum carbide) into an iron-based surfacing material taking Mo2FeB2 as a reinforcing phase, so that the hardness and wear resistance of the surfacing metal are effectively improved; CN106271208B discloses a nickel-based self-fluxing hard-surface surfacing flux-cored wire for plasma surfacing, which has high bonding strength and hardness of a surfacing layer and extremely strong hard-surface wear resistance, abrasive wear resistance and erosion wear resistance, a patent CN104289826B discloses a boride wear-resistant surfacing flux-cored wire and a preparation method thereof, a patent CN108747082B discloses a wear-resistant flux-cored wire and a preparation method thereof, but still takes the flux-cored wire as a main research target, the flux-cored wire can react to form ternary boride under the action of surface modification processes (such as surfacing, spraying and the like), and is influenced by the rapid heating and cooling characteristics of the surface modification process, so that the formation time of the ternary boride is insufficient, the expected effect cannot be achieved, and the requirement of large-scale production is lacked, therefore, the design of integration of the formation of the ternary boride and the formation of the welding rod is lacked, and no good solution is provided for solving the problems of the defects of welding wire component uniformity, tissue homogenization, coating cracking and the like.
Disclosure of Invention
The invention aims to: in order to solve the problems that the flux-cored wire is influenced by the rapid heating and rapid cooling characteristics of a surface modification process, the formation time of a ternary boride hard phase is insufficient, the expected effect cannot be achieved, and the large-scale production needs are lacked, the preparation method of the ternary boride hard alloy surfacing welding rod is provided, the sintered welding rod can make up the defects that the content of the ternary boride hard phase of the flux-cored wire is small and the distribution is uneven, the production efficiency is improved by utilizing an integrated process of forming and sintering the welding rod to generate the ternary boride in situ, and the flux-cored wire has the advantages of strong bonding property of a coating and a steel substrate, high stability of the coating, simple manufacturing equipment, short production period and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a ternary boride hard alloy surfacing electrode specifically comprises the following steps:
s1, processing raw materials, namely putting the metal powder of ferroboron powder, ferrochrome powder, molybdenum powder and iron powder and a small amount of carbon nano tubes or silicon nitride whiskers into a ball mill according to the formula ratio, performing ball milling for 10-20 hours, and mixing the ball-milled powder to obtain ternary boride raw material alloy powder;
s2, preparing an adhesive, and putting the raw materials into a feeding mixer according to the mass percentage for mixing;
s3, mixing materials, namely putting the prepared ternary boride raw material alloy powder and the binder into a mixing roll for mixing, and putting the mixture into a granulator for granulation to obtain a ternary boride raw material feed;
s4, preparing, namely preparing a rod material with a certain length by a molten feed through a round hole die, and preparing the rod material with a certain length by a single-screw forming machine;
and S5, sintering, namely feeding the extruded and molded bar stock into a vacuum sintering furnace, and obtaining the ternary boride hard alloy surfacing electrode by utilizing a sintering process.
As a further description of the above technical solution: the method can realize the sufficient mixing and sintering molding of the ternary boride raw material alloy powder and meet the welding requirement.
Furthermore, the independent particle size of the ternary boride raw material alloy powder is 2-100 mu m.
As a further description of the above technical solution: the independent particle size of the ternary boride raw material is 5-40 mu m, and the ternary boride raw material alloy powder is fully mixed.
Further, the binder comprises the following components in percentage by mass: 20-30% of semi-refined paraffin, 20-30% of white beeswax, 12-18% of high-density polyethylene, 12-18% of TPEE, 15-20% of stearic acid, 0.5-1% of nonionic polyacrylamide and 0.1-1% of oleic acid.
As a further description of the above technical solution: the amount of binder formulated is such as to achieve sufficient binding of the powder.
Furthermore, the mass ratio of the binder in the feeding process is controlled to be 10-20%.
As a further description of the above technical solution: the gripping force of the feed during extrusion is ensured, and the raw material falling caused by excessive materials is avoided.
Furthermore, the temperature in the mixing process is 160-180 ℃, the time is 4-6 h, and the rotating speed of the mixing roll is 60-80 r/min.
As a further description of the above technical solution: improve the material mixing precision.
Further, when a certain bar is extruded and formed by the single-screw extrusion forming machine in the S4, the material temperature is 140-180 ℃, and the extrusion pressure is 20-40 Mpa.
As a further description of the above technical solution: ensure the forming effect during extrusion
Further, the sintering process in S5 comprises the steps of heating to 200-250 ℃ at a speed of 5-10 ℃/min, preserving heat for 1-2 h, heating to 450-500 ℃ at a speed of 5-10 ℃/min, preserving heat for 2-4 h, heating to 800-1100 ℃ at a speed of 5-8 ℃/min, preserving heat for 1-2 h, heating to 1200-1400 ℃ at a speed of 3-5 ℃/min, preserving heat for 0.5-1 h, and cooling in a furnace.
As a further description of the above technical solution: the in-situ reaction after sintering and forming is ensured to form uniformly distributed ternary boride hard phase and the integral strength of the welding rod.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, when the binder is prepared, the wax-based binder with low melting point and good fluidity is selected according to the characteristics of the ternary boride raw material alloy powder, and different alloy element mass fractions are selected from the ternary boride raw material alloy powder to control the final sintering temperature.
In conclusion, compared with the prior art, the ternary boride hard alloy surfacing electrode prepared by the invention has the following characteristics: the diameter and the length of the ternary boride hard alloy surfacing electrode can be flexibly adjusted, the ternary boride surfacing electrode prepared by the method has uniform structure and components, the prepared coating has excellent performance, the dilution rate of the base metal is low, the coating quality is stable, the preparation cost is low, and the operation is simple.
Drawings
FIG. 1 is a process flow chart of a preparation method of a ternary boride hard alloy surfacing electrode;
FIG. 2 is a microstructure of the cross section of a ternary boride cemented carbide coating on the surface of 1Cr13 stainless steel;
figure 3 is an X-ray diffraction (XRD) pattern of a ternary boride cemented carbide coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1-3, the present invention provides a technical solution:
a preparation method of a ternary boride hard alloy surfacing electrode specifically comprises the following steps: A. after ball milling of ternary boride hard alloy raw material powder for 10 hours, the average particle size is 21.5 mu m, and the raw materials comprise the following components in percentage by mass: 20-30 wt% of FeB powder, 8-10 wt% of ferrochrome powder, 30-40 wt% of Mo powder, 1-3 wt% of Ni powder, 1.2-3 wt% of CNTs powder and the balance of Fe powder.
B. Mixing materials: preparing a binder: according to the mass percentage, 25 percent of semi-refined paraffin, 25 percent of white beeswax, 15 percent of high-density polyethylene, 15 percent of TPEE, 19 percent of stearic acid, 0.5 percent of non-ionic polyacrylamide, 0.5 percent of oleic acid and 10 percent of binder are put into a feeding mixing machine, the feeding mixing temperature is 180 ℃, the time is 6 hours, and the rotating speed of the mixing machine is 60 r/min.
C. Forming: heating and extruding the feed by using a single-screw extrusion molding machine, making the molten feed into a bar material with a certain length through a round hole die, and extruding and molding the material at the temperature of 160 ℃ and the extrusion pressure of 20 Mpa.
D. And (3) sintering: and (3) putting the extruded bar into a vacuum sintering furnace, heating to 200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, then heating to 500 ℃ at the speed of 5 ℃/min, preserving heat for 3h, then heating to 950 ℃ at the speed of 6 ℃/min, preserving heat for 1.5h, finally preserving heat for 0.5h at the speed of 3 ℃/min to 1250 ℃, and then cooling along with the furnace.
1Cr13 martensitic stainless steel is selected as a steel substrate, and the steel substrate comprises the following main chemical elements in percentage by weight: 0.12% C, 12% Cr, 0.8% Mn, 0.6% Si, Ni: 0.5 and Fe: and the rest is that the sintered ternary boride hard alloy electrode is used for forming a high-hardness and high-wear-resistance coating on the surface of the 1Cr13 martensitic stainless steel by using a surfacing process.
In the embodiment, the overall strength of the formed welding rod is ensured by adjusting the extrusion pressure, the sintering temperature is controlled by integrating degreasing and sintering and multi-stage heating, the strength of the sintered welding rod is improved, and the defects of deformation, cracks and the like of a welding rod blank in the heating and sintering processes are avoided.
Example 2
Different from the embodiment 1, the embodiment discloses a preparation method of a ternary boride hard alloy surfacing electrode, which specifically comprises the following steps: A. after ball milling for 15 hours, the average particle size of the ternary boride hard alloy raw material powder is 16.5 mu m, and the raw material comprises 25-40 wt% of FeB powder, 5-8 wt% of ferrochrome powder, 35-50 wt% of Mo powder, 2-5 wt% of Ni powder, 2.5-5 wt% of Si powder3N4The balance of powder and Fe powder.
B. Mixing materials: preparing a binder: according to the mass percentage, 23 percent of semi-refined paraffin, 25 percent of white beeswax, 15 percent of high-density polyethylene, 15 percent of TPEE, 10 percent of stearic acid, 1 percent of non-ionic polyacrylamide, 1 percent of oleic acid and 20 percent of binder are put into a feeding mixing machine, the feeding mixing temperature is 180 ℃, the time is 6 hours, and the rotating speed of the mixing machine is 60 r/min.
C. Forming: heating and extruding the feed by using a single-screw extrusion molding machine, making the molten feed into a bar material with a certain length through a round hole die, and extruding and molding the material at the temperature of 160 ℃ and the extrusion pressure of 20 Mpa.
D. And (3) sintering: and (3) putting the extruded bar into a vacuum sintering furnace, heating to 250 ℃ at the speed of 8 ℃/min, preserving heat for 2h, then heating to 450 ℃ at the speed of 8 ℃/min, preserving heat for 2h, heating to 1100 ℃ at the speed of 5 ℃/min, preserving heat for 1h, finally preserving heat for 1h at the speed of 4 ℃/min to 1300 ℃, and then cooling along with the furnace.
GCr15 steel is selected as a base material, and the percentage of main chemical elements (wt%) is as follows: 0.95-1.05% of C, 1.30-1.65% of Cr, 0.20-0.40% of Mn, 0.15-0.35% of Si, Ni: less than or equal to 0.30, S: less than or equal to 0.02, P: less than or equal to 0.027, Mo: 0.10 or less and Fe: and the rest is that the sintered ternary boride hard alloy welding rod forms a high-hardness high-wear-resistance coating on the surface of the GCr15 steel by using a surfacing process.
In the embodiment, the ternary boride hard alloy surfacing welding electrode is prepared based on a powder metallurgy technology and a single-screw extrusion molding technology, firstly, ternary boride raw material alloy powder is respectively mixed with a binder, and then, the molten ternary boride raw material alloy powder is fed by pressure in a single-screw extrusion molding mode to be prepared into a green welding electrode blank through a die; finally sintering and densifying to obtain the ternary boride hard alloy surfacing electrode, wherein the proportion of the ternary boride raw material and the binder and the degreasing and sintering temperatures are key steps of the invention, and the performance of the final electrode is determined.
And (3) verification experiment:
the ternary boride/stainless steel composite structure obtained in the example was analyzed, and the cross-sectional metallographic structure of the sample was observed under a multifunctional zeiss axioplan2 type Optical Microscope (OM) (fig. 2); phase analysis of the ternary boride layer by means of an X-ray diffractometer (XRD) of the X' PertProMPD type (using Cu target Ka rays, step size 0.02 ℃ C.) (FIG. 3); measuring the microhardness of a sample by using an HX-500 microhardness meter, and respectively taking 5 points to measure the hardness to obtain the average Vickers hardness of the stainless steel substrate and the ternary boride layer, wherein the loading force is 500gf, and the load retention time is 10 s; carrying out abrasion test (rotating speed 100r/min, load 100N and abrasion time 8h) by adopting a UG-10Z type abrasion tester; tensile strength was measured using a universal tester as a standard for evaluating the bonding strength (hardness, bonding strength and abrasion resistance are shown in table 1).
FIG. 2 is a microstructure of a cross-section of a ternary boride cemented carbide coating on the surface of 1Cr13 stainless steel obtained in example 1, the ternary boride cemented carbide coating has good bonding condition with a 1Cr13 stainless steel substrate, no obvious cracks and holes at the bonding position, uniform tissue distribution in the coating and no macro defects such as pores, undercut and cracks, FIG. 3 is an X-ray diffraction (XRD) diagram of the ternary boride cemented carbide coating, and the microstructure of the ternary boride cemented carbide coating is obtained from Mo2FeB2、α-Fe、(Mo,Cr,Fe)3B2And (Cr, Fe)7C3Composition of, wherein Mo2FeB2The highest diffraction peak indicates that the substance has the highest specific gravity and the highest quantity in the coating, which indirectly indicates that the coating has higher hardness and strength, (Mo, Cr, Fe)3B2And (Cr, Fe)7C3As the hard phase, the hardness of the coating can be effectively improved, and the alpha-Fe is used as the binder phase, so that the toughness of the coating can be ensured, the hard phase can be supported, the hard particles can be effectively prevented from being peeled off, and the wear resistance is enhanced.
Table 1 examples 1-2 hardness, bond strength and abrasion resistance
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of a ternary boride hard alloy surfacing electrode is characterized by comprising the following steps:
s1, processing raw materials, namely putting the metal powder of ferroboron powder, ferrochrome powder, molybdenum powder and iron powder and a small amount of carbon nano tubes or silicon nitride whiskers into a ball mill according to the formula ratio, performing ball milling for 10-20 hours, and mixing the ball-milled powder to obtain ternary boride raw material alloy powder;
s2, preparing an adhesive, and putting the raw materials into a feeding mixer according to the mass percentage for mixing;
s3, mixing materials, namely putting the prepared ternary boride raw material alloy powder and the binder into a mixing roll for mixing, and putting the mixture into a granulator for granulation to obtain a ternary boride raw material feed;
s4, preparing, namely preparing a rod material with a certain length by a molten feed through a round hole die, and preparing the rod material with a certain length by a single-screw forming machine;
and S5, sintering, namely feeding the extruded and molded bar stock into a vacuum sintering furnace, and obtaining the ternary boride surfacing electrode by using a sintering process.
2. The method for preparing the ternary boride cemented carbide surfacing electrode according to claim 1, characterized in that the ternary boride raw material alloy powder has an independent particle size of 2 to 100 μm.
3. The method for preparing a ternary boride cemented carbide surfacing electrode according to claim 1, characterized in that the binder is, by mass: 20-30% of semi-refined paraffin, 20-30% of white beeswax, 12-18% of high-density polyethylene, 12-18% of TPEE, 15-20% of stearic acid, 0.5-1% of nonionic polyacrylamide and 0.1-1% of oleic acid.
4. The method for preparing a ternary boride cemented carbide surfacing electrode according to claim 1, characterized in that the mass ratio of the binder in the feeding process is controlled between 10% and 20%.
5. The preparation method of the ternary boride hard alloy surfacing electrode according to claim 1, characterized in that the temperature in the mixing process is 160-180 ℃, the time is 4-6 h, and the rotating speed of a mixing mill is 60-80 r/min.
6. The method for preparing the ternary boride hard alloy surfacing electrode according to claim 1, wherein when a certain bar is extruded and molded by a single-screw extrusion molding machine in S4, the material temperature is 140-180 ℃, and the extrusion pressure is 20-40 Mpa.
7. The preparation method of the ternary boride hard alloy surfacing welding electrode according to claim 1, characterized in that the sintering process in S5 is heating to 200-250 ℃ at a speed of 5-10 ℃/min, preserving heat for 1-2 h, then heating to 450-500 ℃ at a speed of 5-10 ℃/min, preserving heat for 2-4 h, then heating to 800-1100 ℃ at a speed of 5-8 ℃/min, preserving heat for 1-2 h, finally heating to 1200-1400 ℃ at a speed of 3-5 ℃/min, preserving heat for 0.5-1 h, and then cooling with a furnace.
8. A ternary boride cemented carbide surfacing electrode, characterized by being prepared by the method for preparing a ternary boride cemented carbide surfacing electrode according to any one of claims 1 to 7.
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