CN114150199A - Hard alloy material, hard alloy machine barrel and surface treatment method thereof - Google Patents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/68—Barrels or cylinders
- B29C48/6801—Barrels or cylinders characterised by the material or their manufacturing process
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
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Abstract
The invention relates to a hard alloy material, a hard alloy machine barrel and a surface treatment method thereof, wherein the material comprises the following components in percentage by weight: cobalt powder accounting for 8-10% of the total weight; nickel powder, which accounts for 2-3% of the total weight; rare earth neodymium accounting for 0.08-0.1% of the total weight; rare earth praseodymium accounting for 0.04-0.08% of the total weight; chromium carbide accounting for 2-4% of the total weight; the rest components are tungsten carbide. The beneficial effects are that: the invention uses Ni (2-3%), Nd (0.08-0.1%), Pr (0.04-0.08%), Cr3C2(2-4%) components together play a synergistic role, so that the recrystallization resistance in the structure transformation process of the alloy sintered body is increased, the number of liquid phases in the alloy sintered body and the uneven growth of tungsten carbide crystal grain size are inhibited, the sensitivity of the alloy to the carbon content is reduced, and the phase can be changedThe control difficulty of the alloy sintering process is reduced.
Description
Technical Field
The invention specifically relates to the technical field of alloy materials, and specifically relates to a hard alloy material, a hard alloy machine barrel and a surface treatment method thereof.
Background
The screw extruder is a mechanical production device widely applied to industries such as plastic, food and feed processing, and the like, and the working principle of the screw extruder is that pressure and shearing force are generated through rotation of a screw, so that materials are subjected to physical or chemical changes after the actions of mixing, extruding, shearing and the like, and finally, a finished product is extruded at the terminal of the device.
With the continuous progress of lithium ion battery materials, the particle size of raw material particles is smaller and smaller, so that the performance of the lithium ion battery is improved, and secondary aggregates are easy to form, thereby increasing the difficulty of a mixing and dispersing process. The full-automatic double-screw continuous homogenizing process is used as a novel alternative process, and is particularly suitable for producing high-capacity, high-power, high-stability and high-dispersity lithium battery electrode slurry. The homogenizing screw element and the barrel/liner are the core components of a twin-screw continuous homogenizing process, and the following challenges are faced during the complicated homogenizing work:
a) and due to frequent collision and friction among materials and friction between a homogenizing part and the materials, the machine barrel can generate simultaneous comprehensive effects of four wear types, namely fatigue wear, corrosive wear, adhesive wear and abrasive wear under the long-term action of the machine barrel and slurry. Therefore, the service life of a machine barrel of the double-screw extruder is shortened, and the residual scraps of the worn parts enter electrode slurry to cause adverse effects on the structural components and the purity of the lithium battery.
b) Corrosion, corrosion is defined as the chemical or electrochemical reaction that occurs between a material and its environment, leading to deterioration of the material and its properties. For a pulping system in which the cell material is in a thermodynamically non-equilibrium state, the electrolyte is in contact with the surface of the homogenizing part for a long period of time and is highly susceptible to galvanic corrosion, i.e., oxidation of Li to Li +, with changes in temperature, viscosity, etc. Due to the locally enhanced electro-dissolution effect of the lithium particles, pores are formed on the metal surface, resulting in severe degradation of the local material. Therefore, the material of the cylinder is required to have stronger corrosion resistance, wear resistance and stable physical and chemical properties.
c) The slurry is sticky, and in the preparation process, in order to increase the bonding force with the film in the subsequent coating process of coating, a proper adhesive is often mixed in the slurry. Slurries are very complex suspension systems containing a large percentage of solid particles of different chemical substances, sizes and shapes in a high viscosity medium. The viscosity of the polymer binder solution affects the coating properties, which affects the ease with which the powder is dispersed, the power required for mixing, and the speed of application of a uniform coating. To reduce frictional resistance during homogenization, reduce energy consumption, reduce wear and corrosion of parts, and maintain cleanliness, the barrel is required to have a lower surface energy and surface tension, thereby reducing adhesion between the electrode slurry and the barrel.
Disclosure of Invention
The invention aims to solve the problems and provide a hard alloy cylinder and a surface treatment method thereof, a small amount of rare earth is added into the hard alloy cylinder, the metallographic structure and the grain uniformity are improved, the surface tension is reduced by roughening the roughness of the inner surface of the cylinder by a laser technology, and the cylinder obtained by the invention has the advantages of high toughness, high hardness, high wear resistance, high corrosion resistance, low surface tension and the like, and can greatly improve the production efficiency and the product quality of lithium battery slurry.
The purpose of the invention is realized by the following technical scheme:
the hard alloy material comprises the following components in percentage by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-3% of the total weight;
rare earth neodymium accounting for 0.08-0.1% of the total weight;
rare earth praseodymium accounting for 0.04-0.08% of the total weight;
chromium carbide accounting for 2-4% of the total weight;
the rest components are tungsten carbide.
Further, the hard alloy material comprises the following components in percentage by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-2.5% of the total weight;
rare earth neodymium accounting for 0.08-0.09% of the total weight;
the rare earth praseodymium accounts for 0.06-0.07% of the total weight;
chromium carbide accounting for 2-3.5% of the total weight;
the rest components are tungsten carbide.
0.08-0.1% of rare earth element Nd is added into the hard alloy material, so that the addition of the rare earth element can inhibit the transformation of alpha-Co in the alloy to an epsilon-Co phase (hcp structure), the alpha-Co phase (fe structure) in a binding phase is improved from 60% to about 95%, the grain size is more uniform and finer, namely the Co phase is uniformly distributed, and the average area of the Co phase is reduced to 0.4 mu m2Below, the length and width are also reduced to below 0.6 μm and 0.5 μm, thereby improving the wear resistance, toughness and impact resistance of the barrel.
0.04-0.08% of rare earth element Pr is added into the hard alloy material, and the Pr element participates in the alloying process to reduce the eutectic temperature, so that the melting point of the binder phase is reduced by about 30 ℃, and the liquid phase occurrence temperature is reduced.
2-3% of nickel powder is added into the hard alloy material, the average particle size of the nickel powder is about 0.5 mu m, so that the liquid phase proportion is increased in the sintering process, the fluidity is relatively enhanced, and micropores are compressed and the diameter of the micropores is gradually reduced; in addition, WC crystal grains grow up moderately with the increase of liquid phase, and micropores around the WC crystal grains are extruded, so that the density of the alloy is increased, the porosity of the hard alloy cylinder is reduced, and the bending strength and the corrosion resistance of the cylinder are further improved.
The invention also provides a hard alloy machine barrel which is made of the hard alloy material, and the hard alloy machine barrel comprises the following materials in parts by weight:
cobalt (Co) powder accounting for 8-10% of the total weight;
nickel (Ni) powder accounting for 2-3% of the total weight;
rare earth neodymium (Nd) accounting for 0.08-0.1% of the total weight;
rare earth praseodymium (Pr) accounting for 0.04-0.08 percent of the total weight;
chromium carbide (Cr)3C2) Accounting for 2-4% of the total weight;
the rest components are tungsten carbide (WC).
Further, the hard alloy cylinder comprises the following materials in percentage by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-2.5% of the total weight;
rare earth neodymium accounting for 0.08-0.09% of the total weight;
the rare earth praseodymium accounts for 0.06-0.07% of the total weight;
chromium carbide accounting for 2-3.5% of the total weight;
the rest components are tungsten carbide.
The invention also provides a surface treatment method of the hard alloy machine barrel, which comprises the following treatment steps:
step 01, polishing and cleaning;
polishing the surface of the hard alloy cylinder by using a diamond grinding wheel on a polishing machine; placing the polished hard alloy machine barrel into an ultrasonic oscillation cleaning machine, sequentially cleaning the hard alloy machine barrel with acetone, absolute ethyl alcohol and deionized water for 5min respectively, and drying the hard alloy machine barrel with nitrogen;
step 02, laser scanning, namely placing the cleaned hard alloy cylinder on a laser processing machine tool, and performing laser scanning processing on the inner surface of the hard alloy cylinder through set processing frequency, scanning speed and processing power;
and 03, cleaning again, namely washing the hard alloy cylinder processed by laser scanning with deionized water, then putting the hard alloy cylinder into an ultrasonic cleaning machine to clean and remove residual processing dust on the surface, and finally drying the cleaned hard alloy cylinder.
Further, the frequency range of the laser processing in the step 02 is 35-45 kHz.
Further, the laser scanning speed range of the laser processing in the step 02 is 650-750 mm/s.
Further, the frequency laser processing power of the laser processing in the step 02 is 150-.
Further, the frequency range of the laser processing in the step 02 is 38-40 kHz.
Further, the laser scanning speed range of the laser processing in the step 02 is 700-720 mm/s.
Further, the laser processing power in the step 02 is 150-.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses Ni (2-3%), Nd (0.08-0.1%), Pr (0.04-0.08%), Cr3C2(2-4%) of the components are used together to play a synergistic effect, so that the recrystallization resistance in the structure transformation process of the alloy sintered body is increased, the number of liquid phases in the alloy sintered body and the uneven growth of tungsten carbide crystal grain size are inhibited, the sensitivity of the alloy to the carbon content is reduced, and the control difficulty in the alloy sintering process can be correspondingly reduced.
(2) According to the invention, through the synergistic interaction of the processing technologies such as laser processing frequency (38-40 Hz), laser processing power (150-170W), laser scanning speed (700-720 mm/s) and the like, the inner surface of the machine barrel is provided with a micron-sized microporous structure, the contact angle is improved to the maximum extent by increasing the roughness of the inner surface of the machine barrel, the contact area between the machine barrel and lithium battery slurry can be reduced, and the anti-sticking effect is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive exercise.
Fig. 1 is a crystal phase diagram of the surface of a cemented carbide material of example 13.
FIG. 2 is a graph of the effect of Pr content on WC grain size in the alloy.
FIG. 3 shows Cr3C2Graph of the effect of content on WC grain size in the alloy.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
The hard alloy material comprises the following components in percentage by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-3% of the total weight;
rare earth neodymium accounting for 0.08-0.1% of the total weight;
rare earth praseodymium accounting for 0.04-0.08% of the total weight;
chromium carbide accounting for 2-4% of the total weight;
the rest components are tungsten carbide.
0.08-0.1% of rare earth element Nd is added into the hard alloy material, so that the addition of the rare earth element can inhibit the transformation of alpha-Co in the alloy to an epsilon-Co phase (hcp structure), the alpha-Co phase (fe structure) in a binding phase is improved from 60% to about 95%, the grain size is more uniform and finer, namely the Co phase is uniformly distributed, and the average area of the Co phase is reduced to 0.4 mu m2Below, the length and width are also reduced to below 0.6 μm and 0.5 μm, thereby improving the wear resistance, toughness and impact resistance of the barrel.
0.04-0.08% of rare earth element Pr is added into the hard alloy material, and the Pr element participates in the alloying process to reduce the eutectic temperature, so that the melting point of the binder phase is reduced by about 30 ℃, and the liquid phase occurrence temperature is reduced.
2-3% of nickel powder is added into the hard alloy material, the average particle size of the nickel powder is about 0.5 mu m, so that the liquid phase proportion is increased in the sintering process, the fluidity is relatively enhanced, and micropores are compressed and the diameter of the micropores is gradually reduced; in addition, WC crystal grains grow up moderately with the increase of liquid phase, and micropores around the WC crystal grains are extruded, so that the density of the alloy is increased, the porosity of the hard alloy cylinder is reduced, and the bending strength and the corrosion resistance of the cylinder are further improved.
TABLE 1
From Table 1, comparing the impact toughness and corrosion potential results of the alloys of examples 1, 2, 3 and 4 with those of comparative examples 1, 2, 3 and 4 at different Ni contents, it can be seen that the higher the Ni content, the higher the corrosion potential of the alloy, but the impact resistance of the alloy is significantly reduced, and the impact toughness is reduced to 22.6J-cm-2Obviously, the alloy machine barrel is not beneficial to dealing with the harsh working condition of the double-screw extruder, and the Ni content of 2-3% has higher corrosion potential and better impact toughness.
TABLE 2
From table 2, comparing the impact toughness and corrosion potential results of the alloys with different Nd contents in examples 5, 6, 7 and 8 and comparative examples 5, 6, 7 and 8, it is known that the corrosion potential of the alloy is significantly reduced when the Nd content is below 0.08%, the corrosion resistance of the alloy is reduced, and both the corrosion potential and impact toughness of the alloy are reduced when the Nd content is above 0.1%, which is not good for the corrosion resistance and impact resistance of the alloy. Nd with the content of 0.08-0.1% is the preferable proportion for realizing good physical and chemical properties of the alloy.
TABLE 3
From table 3, comparing the impact toughness and corrosion potential results of the alloys of examples 8, 9 and 10 with those of comparative examples 9, 10, 11 and 12 at different Pr contents, it can be seen from fig. 2 that the corrosion potential of the alloys is reduced significantly when the Pr content exceeds the range of 0.04-0.08%.
TABLE 4
From Table 4, Cr is different in examples 11, 12, 13, and 14 from that in comparative examples 13, 14, 15, and 163C2The impact toughness and corrosion potential results of the alloy at the content are compared, and as can be seen from FIG. 3, Cr3C2The lower the corrosion potential of the alloy, the lower the Cr content3C2The higher the content, the lower the impact toughness of the alloy, and Cr3C2The content is within the range of 2-4%, and the composite material has better comprehensive performance.
Referring to fig. 1, a microstructure of embodiment 13 having a micro-porous structure of a micron order can reduce a contact area of a cylinder with a lithium battery paste, thereby achieving an anti-sticking effect.
Therefore, the invention is characterized by comprising 2-3% of Ni, 0.08-0.1% of Nd, 0.04-0.08% of Pr and Cr3C2(2-4%) of the components together play a synergistic effect, so that the recrystallization resistance in the structure transformation process of the alloy sintered body is increased, the number of liquid phases in the alloy sintered body and the uneven growth of tungsten carbide crystal grain size are inhibited, the sensitivity of the alloy to the carbon content is reduced, and the control difficulty in the alloy sintering process can be correspondingly reduced.
The invention also provides a surface treatment method of the hard alloy machine barrel, which comprises the following steps: the cemented carbide barrels made using the material composition described above for example 13 were subjected to the following processing steps:
step 01, polishing and cleaning;
polishing the surface of the hard alloy cylinder by using a diamond grinding wheel on a polishing machine; placing the polished hard alloy machine barrel into an ultrasonic oscillation cleaning machine, sequentially cleaning the hard alloy machine barrel with acetone, absolute ethyl alcohol and deionized water for 5min respectively, and drying the hard alloy machine barrel with nitrogen;
step 02, laser scanning, namely placing the cleaned hard alloy cylinder on a laser processing machine tool, and performing laser scanning processing on the inner surface of the hard alloy cylinder through set processing frequency, scanning speed and processing power;
and 03, cleaning again, namely washing the hard alloy cylinder processed by laser scanning with deionized water, then putting the hard alloy cylinder into an ultrasonic cleaning machine for cleaning for 5min to remove residual processing dust on the surface, and finally drying the cleaned hard alloy cylinder in a constant temperature box.
The results under different conditions are illustrated below in specific comparative examples.
TABLE 5
As shown in Table 5, when the contact angles of the inner surfaces of the barrels at different processing frequencies are compared with those of the examples 1 to 5 and the comparative examples 1 to 4, the contact angle of the inner surface of the barrel at the laser processing frequency within the range of 38 to 40Hz with water is larger, and the anti-sticking effect is more excellent.
TABLE 6
As shown in Table 6, when the contact angles of the inner surfaces of the barrels at different processing frequencies are compared with those of the examples 6 to 9 and the comparative examples 5 to 9, the contact angle of the inner surface of the barrel with water at the laser processing power ranging from 150W to 170W is larger, and the anti-sticking effect is more excellent.
TABLE 7
As shown in Table 7, the contact angles of the inner surface of the cylinder at the laser scanning speeds of 700 to 720mm/s are larger than those of the inner surface of the cylinder at the laser scanning speeds of 10 to 13 and 10 to 13 in comparison with the inner surface of the cylinder at different laser scanning speeds.
According to the invention, through the synergistic interaction of the processing technologies such as laser processing frequency (38-40 Hz), laser processing power (150-170W), laser scanning speed (700-720 mm/s) and the like, the inner surface of the machine barrel is provided with a micron-sized microporous structure, the contact angle is improved to the maximum extent by increasing the roughness of the inner surface of the machine barrel, the contact area between the machine barrel and lithium battery slurry can be reduced, and the anti-sticking effect is good.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A cemented carbide material characterized by: the hard alloy material comprises the following components in percentage by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-3% of the total weight;
rare earth neodymium accounting for 0.08-0.1% of the total weight;
rare earth praseodymium accounting for 0.04-0.08% of the total weight;
chromium carbide accounting for 2-4% of the total weight;
the rest components are tungsten carbide.
2. The cemented carbide material of claim 1, wherein the cemented carbide material comprises the following materials in parts by weight:
cobalt powder accounting for 8-10% of the total weight;
nickel powder, which accounts for 2-2.5% of the total weight;
rare earth neodymium accounting for 0.08-0.09% of the total weight;
the rare earth praseodymium accounts for 0.06-0.07% of the total weight;
chromium carbide accounting for 2-3.5% of the total weight;
the rest components are tungsten carbide.
3. A hard alloy barrel is characterized in that: the cemented carbide barrel consisting of the cemented carbide material of claim 1 or 2.
4. A method for the surface treatment of a cemented carbide barrel according to claim 3, characterized by the following treatment steps:
step 01, polishing and cleaning;
step 02, laser scanning, namely placing the cleaned hard alloy cylinder on a laser processing machine tool, and performing laser scanning processing on the inner surface of the hard alloy cylinder through set processing frequency, scanning speed and processing power;
and 03, cleaning again, namely washing the hard alloy cylinder subjected to laser scanning processing by using deionized water, then putting the hard alloy cylinder into an ultrasonic cleaning machine to clean and remove residual processing dust on the surface, and finally drying the cleaned hard alloy cylinder.
5. The method of claim 4, wherein the method comprises the following steps: the frequency range of laser processing in the step 02 is 35-45 kHz.
6. The method of claim 4, wherein the method comprises the following steps: the laser scanning speed range of the laser processing in the step 02 is 650-750 mm/s.
7. The method of claim 4, wherein the method comprises the following steps: the frequency laser processing power of the laser processing in the step 02 is 150-200W.
8. The method of claim 5, wherein the method comprises the following steps: the frequency range of laser processing in the step 02 is 38-40 kHz.
9. The method of claim 6, wherein the method comprises the following steps: the laser scanning speed range of the laser processing in the step 02 is 700-720 mm/s.
10. The method of claim 7, wherein the method comprises the following steps: the laser processing power in the step 02 is 150-170W.
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