CN115464136B - Preparation method of high-purity electrode for spherical copper-chromium alloy powder process - Google Patents
Preparation method of high-purity electrode for spherical copper-chromium alloy powder process Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-purity electrode for a spherical copper-chromium alloy powder process, which comprises the following steps: s1, compounding carbon, S2, sintering and degassing, S3, crushing and pulverizing, S4, compounding copper and chromium, S5, cold isostatic pressing, S6, bar alloying, S7 and machining. The invention adopts the powder metallurgy technology to prepare the copper-chromium alloy electrode, has low gas content, less inclusion and good uniformity and consistency of the electrode, and the prepared electrode bar is close enough to the electrode required by EIGA and PREP in size, so the turning quantity is very small, and the utilization rate of raw materials can be effectively improved.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a preparation method of a high-purity electrode for a spherical copper-chromium alloy powder process.
Background
In order to meet the requirements of additive manufacturing equipment and process, the metal powder must have the characteristics of low oxygen and nitrogen content, good sphericity, narrow particle size distribution interval, high apparent density and the like. Plasma Rotary Electrode Process (PREP), plasma atomization Process (PA), vacuum induction melting gas atomization (VIGA), vacuum induction electrode gas atomization (EIGA), and plasma spheroidization Process (PS) are the main processes for preparing metal powder for additive manufacturing at present, which can all prepare spherical or nearly spherical metal powder, wherein the PREP process and the EIGA process both require electrodes as raw materials.
The PREP method is to process metal or alloy into consumable electrode bar stock, heat the bar end with plasma, rotate the bar stock at high speed, throw out the metal liquid by centrifugal force to form small liquid, solidify in inert gas environment and spheroidize to form powder under the action of surface tension.
The EIGA method combines the gas atomization technology and the electrode induction smelting technology, and has the specific principle that an alloy is processed into a bar stock, the bar stock is arranged on a feeding device, the whole device is vacuumized and filled with inert protective gas, an electrode rod enters a conical coil below the electrode rod at a certain rotation speed and a descending speed, the tip of the bar stock is subjected to induction heating action in the conical coil to be gradually melted to form a melt liquid flow, the melt liquid flow directly flows into or drops into a non-limiting atomizer below the conical coil under the action of gravity, high-pressure inert gas enters the atomizer through a gas circuit pipeline, the interaction is carried out between the high-pressure inert gas and the metal liquid flow below a gas outlet to break the metal liquid flow into small liquid drops, and the small liquid drops are spherical under the action of tension and then solidify into small particles.
Compared with the VIGA meeting which is most widely applied at present, the PREP and VIGA processes have the advantages that parts such as a crucible which is contacted with a metal melt are abandoned, the impurity introduction in the smelting process can be effectively reduced, the air release of the crucible is avoided, and the safe and clean smelting of active metals is realized. Although the two processes have obvious advantages, the introduction of gas and impurities can be effectively controlled in the atomizing and pulverizing process, the preparation process of the electrode used by the electrode can be influenced by smelting, particularly in the high-temperature smelting stage, the quality of the prepared electrode is reduced due to the fact that a crucible is deflated and falls off, for copper-chromium alloy, the impurities are extremely easy to generate due to the fact that copper is corroded on the crucible, meanwhile, chromium has extremely strong oxygen absorption performance, the quality of a copper-chromium electrode rod prepared by adopting a vacuum induction smelting method is lower, in addition, for a copper-chromium electrode added with a special third element, the component uniformity is difficult to ensure due to the fact that the third element with larger difference of melting point, boiling point and density from copper and chromium, the copper-chromium electrode meeting the requirements cannot be prepared, finally, the heat transfer of the copper-chromium electrode in an as-cast state structure can be improved, so that energy consumption is caused in the EIGA process, and even liquid flow cannot be smoothly formed. However, for PREP processes, a higher strength of the electrode itself is required to ensure that the spinning process is sufficiently strong. Finally, the electrode prepared by the smelting method needs to remove riser shrink holes and negative plates, and is subjected to forging deformation treatment so as to reach the required size, the surface of the cast ingot is oxidized and cracked in the forging process, and the surface machining is required by a lathe, so that the utilization rate of raw materials is greatly reduced in all the processes.
The prior art mainly adopts the modes of (1) batching, (2) vacuum induction melting, (3) forging deformation, (4) heat treatment and (5) mechanical processing to prepare the electrode material, and has the following defects: 1) In the vacuum induction smelting process, because the metal melt formed by heating the raw materials contacts with the crucible, the crucible is deflated and falls off; 2) Because copper has strong corrosiveness to the crucible, chromium has extremely strong oxygen absorbing capacity, the purity of the material is further reduced, and the quality of a final electrode is reduced; 3) For the copper-chromium electrode with optimized performance by adding the third element, the copper-chromium electrode is limited by smelting and main components of copper-chromium alloy, and the components and consistency of the third element with low boiling point or high melting point or large density difference are difficult to be effectively and fully ensured; 4) Because copper has good heat conductivity, for some copper-chromium electrodes with higher copper content, the heat dissipation of a smelting area is caused by the good heat dissipation characteristic of an electrode with an as-cast structure in the EIGA powder process, the melting point temperature cannot be reached, and even the problem that an electrode-free rod cannot be melted to form a metal liquid flow is caused, so that extremely high power output is required, and energy waste is caused; 5) The casting electrode preparation process smelting process can generate riser, shrinkage cavity and rough outer wall, and the subsequent forging can also oxidize the skin and have larger machining allowance, and the defects are removed through a lathe and a sawing machine, so that the material waste can be caused, and the utilization rate of raw materials is greatly reduced.
Disclosure of Invention
Aiming at the problems pointed out by the background technology, the invention provides a preparation method of a high-purity electrode for a spherical copper-chromium alloy powder process, which comprises the following steps:
s1, compounding carbon:
taking chromium powder, detecting the oxygen content of the chromium powder, carrying out carbon matching according to the oxygen content of the chromium powder, and carrying out carbon matching according to a reaction equation of thermal carbon reduction to obtain O: c is calculated according to the molar ratio of 1:1 to obtain a carbon proportioning ratio A, the adding amount of carbon powder is added according to 50% -80% of the ratio A, the carbon powder is ensured to be in an under-carbon state, then the chromium powder and the carbon powder are mixed evenly by hand, the carbon powder is observed until the naked eyes cannot see the carbon powder, then the powder is mixed for 1-3 hours by using a mixer, finally the carbon powder and the chromium powder are enabled to collide and adhere evenly on the surface of the chromium powder by using an air flow mill (the air flow mill adopts the prior art), then the adding ratio B of the carbon in the chromium powder is detected by sampling, the carbon powder (A-B) multiplied by 1.05 is replenished, and after the mixture is mixed evenly by hand, the carbon powder is mixed evenly by hand: copper ball = 100:100 weight proportion, ball milling and mixing for 3-10 h, and further crushing and dispersing the agglomerated carbon by ball milling and mixing to ensure uniformity;
s2, sintering and degassing:
pouring the uniformly mixed chromium powder obtained in the step S1 into a graphite crucible in a loose manner, wherein the loose manner can ensure effective duct exhaust, and then placing the chromium powder into a vacuum sintering furnace for vacuum sintering and degassing to obtain a chromium powder blank;
s3, crushing and pulverizing:
crushing and pulverizing the chromium powder blank subjected to sintering and degassing in the step S2 to obtain high-purity low-gas chromium powder with the particle size of 450-830 mu m;
s4, mixing copper and chromium:
the oxygen-free copper powder and the high-purity low-gas chromium powder obtained in the step S3 are proportioned and mixed according to the required proportion to obtain mixed powder A (if the electrode material needs to be added with third elements such as Zr, te and the like, the addition is carried out according to the required proportion), and the mixed powder A is prepared by the following steps: copper ball = 100:100 to obtain mixed powder B, wherein the mixed powder B can ensure the uniformity of mixing copper powder and chromium powder and the effectiveness of adding third element;
s5, cold isostatic pressing:
pressing the mixed powder B obtained in the step S4 in a cold isostatic pressing mode to obtain a bar stock;
s6, bar alloying:
carrying out alloying treatment on the bar stock obtained in the step S5 to obtain a high-purity electrode blank for the spherical copper-chromium alloy powder process;
s7, machining:
and (3) processing the electrode material blank prepared in the step (S6) into a required size according to the drawing requirement, and obtaining the high-purity electrode for the spherical copper-chromium alloy powder process.
Further, in the scheme, the particle size of the carbon powder is 1-6.5 mu m, so that the chromium powder and the carbon powder are effectively ensured to be fully contacted.
Further, in the above scheme, the method of vacuum sintering and degassing in step S2 is as follows: vacuumizing until the vacuum degree in the sintering furnace is below 1Pa, raising the temperature in the vacuum sintering furnace to 300-600 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 20-40 min, so that the gas adsorbed on the surface of the chromium powder is pumped away, raising the temperature in the vacuum sintering furnace to 1400-1500 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 4-8 h.
Description: vacuum sintering refers to a protective sintering method for a green body in a vacuum environment, and heating modes of the green body are relatively large, such as resistance heating, induction heating, microwave heating and the like. The vacuum sintering furnace is a furnace for carrying out protective sintering on heated articles by utilizing induction heating, and can be classified into power frequency, medium frequency, high frequency and the like, and the principle is that elements such as water vapor, hydrogen, oxygen, nitrogen and the like in a green body can escape from air holes along the grain boundary of the green body or through grains by dissolving and diffusing in the sintering process under the vacuum condition, so that the compactness of the product is improved. The reduction of the carbon to the oxide can be realized by vacuum sintering and degassing, a thermal carbon reduction reaction is realized, and the high temperature is utilized to remove low-melting-point impurities and nitrides, so that the purity of the chromium is further improved.
Further, in the above scheme, the method for crushing and pulverizing in step S3 is as follows: crushing by a jaw crusher, and grinding by a vibration mill or an air flow mill.
Description: the working part of the jaw crusher is two jaw plates, one is a fixed jaw plate (fixed jaw), the fixed jaw plate is vertically (or the upper end is slightly inclined outwards) fixed on the front wall of the crusher body, and the other is a movable jaw plate (movable jaw), the position of which is inclined, and a crushing cavity (working cavity) with a large upper part and a small lower part is formed with the fixed jaw plate. The movable jaw moves back and forth periodically against the fixed jaw, and is separated from and close to each other. When the materials are separated, the materials enter the crushing cavity, and the finished products are discharged from the lower part; when approaching, the materials arranged between the two jaw plates are crushed by extrusion, bending and splitting.
The vibration mill utilizes the high-frequency vibration of a cylinder, steel balls or steel rod media in the cylinder impact materials by virtue of inertia force, and the acceleration of the media when impacting the materials can reach 10g-15g, so that the vibration mill has the advantages of compact structure, small volume, light weight, low energy consumption, high yield, concentrated grinding granularity, simplified flow, simple operation, convenient maintenance, easy replacement of lining plate media and the like, and can be widely used for milling powder in industries such as metallurgy, building materials, mines, fire resistance, chemical industry, glass, ceramics, graphite and the like.
The jet mill is characterized in that compressed air is accelerated into supersonic air flow by a Laval nozzle and then is injected into a crushing area to fluidize materials (the air flow expands to form fluidized bed to suspend and boil and collide with each other), so that each particle has the same motion state. In the crushing zone, the accelerated particles collide with each other at the intersection point of the nozzles for crushing. The crushed materials are conveyed to a classification area by an ascending air flow, fine powder meeting the granularity requirement is screened out by a horizontally arranged classification wheel, and coarse powder not meeting the granularity requirement is returned to the crushing area to be continuously crushed. Qualified fine powder enters a high-efficiency cyclone separator along with air flow to be collected, and dust-containing gas is filtered and purified by a dust collector and then is discharged into the atmosphere.
The jaw crusher, the vibration mill, the air flow mill and other equipment are used for crushing and grinding, and the mechanical crushing process is adopted, so that impurities are not introduced and powder reaction is not caused.
Further, in the above scheme, in step S4, the ratio of the oxygen-free copper powder to the high-purity low-gas chromium powder is as follows: cu: cr=99.9: 0.1 to 30:70.
further, in the above scheme, in step S5, the cold isostatic pressing is dry-bag cold isostatic pressing, the pressure of the cold isostatic pressing is controlled to be 100-280 Mpa, and the dwell time is 3-15 min.
Description: the cold isostatic press is to put the materials filled in a sealed elastic mould into a container for containing liquid or gas, apply a certain pressure to the materials by the liquid or gas, and press the materials into a solid body to obtain a blank body with an original shape. After the pressure is released, the mould is taken out from the container, and after demoulding, the blank body is subjected to further shaping treatment according to the requirement. Compared with wet-spraying bag type cold isostatic pressing equipment, the dry bag type cold isostatic pressing equipment has the advantages that the mould is semi-fixed and is not contacted with liquid, so that the straightness of a pressed bar is guaranteed, the cutting amount of subsequent processing can be effectively reduced, the utilization rate of materials is improved, and moisture is effectively prevented from invading copper-chromium bars without being contacted with liquid, so that bar pollution is caused.
Further, in the above scheme, in step S6, the bar alloying treatment is a low-temperature sintering treatment or a hot isostatic pressing treatment.
Alternatively, in the above aspect, the method of the low-temperature sintering treatment is as follows: putting the bar stock obtained in the step S5 into a vacuum sintering furnace, wherein the vacuum reaches 8 multiplied by 10 -1 The pa grade is lower than 300-600 ℃, then inert gas such as argon is filled to micro negative pressure, and the temperature is kept for 2-5 hours at 980-1050 ℃, so that the aim is to alloy bar stock, further desorb adsorbed gas and effectively ensure the effective content of volatile third element.
Description: for the electrode for the EIGA process, the bar stock alloying is carried out in a mode suitable for low-temperature sintering treatment.
Alternatively, in the above solution, the method is characterized by performing the hot isostatic pressing treatment by: firstly, degassing the bar stock obtained in the step S5 by adopting a sheath, wherein the degassing temperature is kept between 300 and 600 ℃, and the vacuum degree is kept to 10 in the degassing process -3 And judging that degassing is finished when Pa is not changed, then clamping a branch exhaust pipeline for hot isostatic pressing, controlling the temperature to be 1000-1050 ℃, controlling the pressure to be 150-350 Mpa and the dwell time to be 1-3 h, and aiming at alloying and improving the compactness of the bar so as to ensure that the bar has enough strength.
Description: for the electrode for the PREP process, the bar stock alloying is carried out in a mode suitable for hot isostatic pressing treatment.
The hot isostatic pressing process is to put the product into a closed container, apply equal pressure to the product in all directions, and apply high temperature at the same time, and sinter and densify the product under the action of high temperature and high pressure. Hot isostatic pressing is an indispensable means for high-performance material production and new material development; the hot isostatic pressing can be directly formed by powder, the powder is filled into a sheath (similar to a die), the sheath can be made of metal or ceramic (low carbon steel, ni, mo, glass and the like), and then nitrogen and argon are used as pressurizing mediums, so that the powder is directly heated, pressed, sintered and formed into the powder metallurgy process; or casting after molding; including aluminum alloys; a titanium alloy; and (3) carrying out thermal densification treatment on castings with shrinkage cavities such as high-temperature alloy, wherein after the thermal isostatic pressing treatment, the castings can reach 100% densification, and the overall mechanical properties of the castings are improved.
Compared with the prior art, the method adopts the powder metallurgy process to prepare the copper-chromium electrode, avoids the possibility of higher gas content and introduction of crucible inclusion caused by contact of raw materials with a crucible, adopts a thermal carbon reduction reaction to further reduce the gas content of the material in the electrode preparation process, and can not prepare the electrode with uniformity due to differences of melting point, boiling point, density and the like for a third element needing to be added.
Detailed Description
Example 1
The preparation method of the high-purity electrode for the spherical copper-chromium alloy powder process comprises the following steps:
s1, compounding carbon:
taking chromium powder, detecting the oxygen content of the chromium powder, carrying out carbon matching according to the oxygen content of the chromium powder, and carrying out carbon matching according to a reaction equation of thermal carbon reduction to obtain O: c, calculating according to a molar ratio of 1:1 to obtain a carbon proportioning ratio A, adding 50% of carbon powder according to the ratio A to ensure that the carbon powder is in an undercarbon state, then manually mixing the chromium powder and the carbon powder until the carbon powder is invisible to naked eyes, mixing the powder for 1h by using a mixer, finally enabling the carbon powder to collide with the chromium powder to be uniformly adhered to the surface of the chromium powder by using an air flow mill, then sampling and detecting the carbon adding ratio B in the chromium powder, supplementing the carbon powder (A-B) multiplied by 1.05, and manually mixing the carbon powder uniformly to obtain the chromium powder: copper ball = 100:100 weight ratio, ball milling and mixing for 3 hours, and further crushing and dispersing the agglomerated carbon by ball milling and mixing to ensure uniformity;
s2, sintering and degassing:
and (3) loosely filling the chromium powder uniformly mixed in the S1 into a graphite crucible, wherein the loosely filling can ensure effective duct exhaust, and then placing the chromium powder into a vacuum sintering furnace for vacuum sintering and degassing: vacuumizing until the vacuum degree in the sintering furnace is below 1Pa, increasing the temperature in the vacuum sintering furnace to 300 ℃ at a heating rate of 3 ℃/min, preserving heat for 20min, so that gas adsorbed on the surface of chromium powder is pumped away, then increasing the temperature in the vacuum sintering furnace to 1400 ℃ at a heating rate of 2 ℃/min, and preserving heat for 4h to obtain a chromium powder blank;
s3, crushing and pulverizing:
crushing and pulverizing the chromium powder blank subjected to sintering and degassing in the step S2 (crushing by adopting a jaw crusher, and grinding by adopting a vibration mill or an air flow mill) to obtain high-purity low-air chromium powder with the particle size of 450-830 mu m;
s4, mixing copper and chromium:
the high-purity low-gas chromium powder obtained by the oxygen-free copper powder and the S3 is prepared from the following components in percentage by weight: cu: cr=99.9: 0.1, and mixing to obtain mixed powder A, (if the electrode material needs to be added with a third element such as Zr, te, etc., the addition is carried out according to the required proportion), and the mixed powder A is prepared according to the following steps: copper ball = 100:100 to obtain mixed powder B, wherein the mixed powder B can ensure the uniformity of mixing copper and chromium powder and the effectiveness of adding a third element;
s5, cold isostatic pressing:
pressing the mixed powder B obtained in the step S4 in a cold isostatic pressing mode, wherein the cold isostatic pressing is dry bag type cold isostatic pressing, the pressure of the cold isostatic pressing is controlled to be 100Mpa, and the pressure maintaining time is 3min, so that a bar stock is obtained;
s6, bar alloying:
and (3) performing low-temperature sintering treatment on the bar material obtained in the step (S5): putting the bar stock obtained in the step S5 into a vacuum sintering furnace, wherein the vacuum reaches 8 multiplied by 10 -1 Degassing below pa level at 300 ℃, then filling inert gases such as argon and the like to slight negative pressure, and preserving heat for 2 hours at 980 ℃ to obtain a high-purity electrode blank for the spherical copper-chromium alloy powder process;
s7, machining:
and (3) processing the electrode material blank prepared in the step (S6) into a required size according to the drawing requirement, and obtaining the high-purity electrode for the spherical copper-chromium alloy powder process.
Example 2
The preparation method of the high-purity electrode for the spherical copper-chromium alloy powder process comprises the following steps:
s1, compounding carbon:
taking chromium powder, detecting the oxygen content of the chromium powder, carrying out carbon matching according to the oxygen content of the chromium powder, and carrying out carbon matching according to a reaction equation of thermal carbon reduction to obtain O: c, calculating according to a molar ratio of 1:1 to obtain a carbon proportioning ratio A, adding carbon powder according to 60% of the ratio A, ensuring that the carbon powder is in an undercarbon state, then manually mixing the chromium powder and the carbon powder until the carbon powder is invisible to naked eyes, mixing the powder for 2 hours by using a mixer, finally enabling the carbon powder to collide with the chromium powder to be uniformly adhered to the surface of the chromium powder by using an air flow mill, then sampling and detecting the carbon adding ratio B in the chromium powder, supplementing the carbon powder (A-B) multiplied by 1.05, and manually mixing the carbon powder uniformly to obtain the chromium powder: copper ball = 100:100 weight ratio, ball milling and mixing for 6 hours, and further crushing and dispersing the agglomerated carbon by ball milling and mixing to ensure uniformity;
s2, sintering and degassing:
and (3) loosely filling the chromium powder uniformly mixed in the S1 into a graphite crucible, wherein the loosely filling can ensure effective duct exhaust, and then placing the chromium powder into a vacuum sintering furnace for vacuum sintering and degassing: vacuumizing until the vacuum degree in the sintering furnace is below 1Pa, increasing the temperature in the vacuum sintering furnace to 500 ℃ at a heating rate of 3 ℃/min, preserving heat for 30min, so that gas adsorbed on the surface of chromium powder is pumped away, then increasing the temperature in the vacuum sintering furnace to 1450 ℃ at a heating rate of 3 ℃/min, and preserving heat for 6h to obtain a chromium powder blank;
s3, crushing and pulverizing:
crushing and pulverizing the chromium powder blank subjected to sintering and degassing in the step S2 (crushing by adopting a jaw crusher, and grinding by adopting a vibration mill or an air flow mill) to obtain high-purity low-air chromium powder with the particle size of 450-830 mu m;
s4, mixing copper and chromium:
the high-purity low-gas chromium powder obtained by the oxygen-free copper powder and the S3 is prepared from the following components in percentage by weight: cu: cr=50: 50, mixing to obtain a mixed powder A (if a third element such as Zr, te is required to be added to the electrode material, the addition is carried out according to a required proportion), and mixing according to the mixed powder A: copper ball = 100:100 to obtain mixed powder B, wherein the mixed powder B can ensure the uniformity of mixing copper and chromium powder and the effectiveness of adding a third element;
s5, cold isostatic pressing:
pressing the mixed powder B obtained in the step S4 in a cold isostatic pressing mode, wherein the cold isostatic pressing is dry bag type cold isostatic pressing, the pressure of the cold isostatic pressing is controlled to be 200Mpa, and the pressure maintaining time is 10min, so that a bar stock is obtained;
s6, bar alloying:
and (3) performing low-temperature sintering treatment on the bar material obtained in the step (S5): putting the bar stock obtained in the step S5 into a vacuum sintering furnace, wherein the vacuum reaches 8 multiplied by 10 -1 Degassing below pa level at 500 ℃, then filling inert gases such as argon and the like to slight negative pressure, and preserving heat for 3 hours at 1000 ℃ to obtain a high-purity electrode blank for the spherical copper-chromium alloy powder process;
s7, machining:
and (3) processing the electrode material blank prepared in the step (S6) into a required size according to the drawing requirement, and obtaining the high-purity electrode for the spherical copper-chromium alloy powder process.
Example 3
The preparation method of the high-purity electrode for the spherical copper-chromium alloy powder process comprises the following steps:
s1, compounding carbon:
taking chromium powder, detecting the oxygen content of the chromium powder, carrying out carbon matching according to the oxygen content of the chromium powder, and carrying out carbon matching according to a reaction equation of thermal carbon reduction to obtain O: c, calculating according to a molar ratio of 1:1 to obtain a carbon proportioning ratio A, adding 80% of carbon powder according to the ratio A to ensure that the carbon powder is in an undercarbon state, then manually mixing the chromium powder and the carbon powder until the carbon powder is invisible to naked eyes, mixing the powder for 3 hours by using a mixer, finally enabling the carbon powder to collide with the chromium powder to be uniformly adhered to the surface of the chromium powder by using an air flow mill, then sampling and detecting the carbon adding ratio B in the chromium powder, supplementing the carbon powder (A-B) multiplied by 1.05, and manually mixing the carbon powder uniformly to obtain the chromium powder: copper ball = 100:100 weight ratio, ball milling and mixing for 10 hours, and further crushing and dispersing the agglomerated carbon by ball milling and mixing to ensure uniformity;
s2, sintering and degassing:
and (3) loosely filling the chromium powder uniformly mixed in the S1 into a graphite crucible, wherein the loosely filling can ensure effective duct exhaust, and then placing the chromium powder into a vacuum sintering furnace for vacuum sintering and degassing: vacuumizing until the vacuum degree in the sintering furnace is below 1Pa, increasing the temperature in the vacuum sintering furnace to 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 40min, so that gas adsorbed on the surface of chromium powder is pumped away, then increasing the temperature in the vacuum sintering furnace to 1500 ℃ at a heating rate of 3 ℃/min, and preserving heat for 8h to obtain a chromium powder blank;
s3, crushing and pulverizing:
crushing and pulverizing the chromium powder blank subjected to sintering and degassing in the step S2 (crushing by adopting a jaw crusher, and grinding by adopting a vibration mill or an air flow mill) to obtain high-purity low-air chromium powder with the particle size of 450-830 mu m;
s4, mixing copper and chromium:
the high-purity low-gas chromium powder obtained by the oxygen-free copper powder and the S3 is prepared from the following components in percentage by weight: cu: cr=30: 70, mixing to obtain a mixed powder A (if a third element such as Zr, te is required to be added to the electrode material, the addition is carried out according to a required proportion), and the mixed powder A is prepared by the following steps: copper ball = 100:100 to obtain mixed powder B, wherein the mixed powder B can ensure the uniformity of mixing copper and chromium powder and the effectiveness of adding a third element;
s5, cold isostatic pressing:
pressing the mixed powder B obtained in the step S4 in a cold isostatic pressing mode, wherein the cold isostatic pressing is dry bag type cold isostatic pressing, the pressure of the cold isostatic pressing is controlled to be 280Mpa, and the pressure maintaining time is 15min, so that a bar stock is obtained;
s6, bar alloying:
and (3) performing low-temperature sintering treatment on the bar material obtained in the step (S5): putting the bar stock obtained in the step S5 into a vacuum sintering furnace, wherein the vacuum reaches 8 multiplied by 10 -1 Degassing below pa level at 600 ℃, then filling inert gases such as argon and the like to slight negative pressure, and preserving heat for 5 hours at 1050 ℃ to obtain a high-purity electrode blank for the spherical copper-chromium alloy powder process;
s7, machining:
and (3) processing the electrode material blank prepared in the step (S6) into a required size according to the drawing requirement, and obtaining the high-purity electrode for the spherical copper-chromium alloy powder process.
The electrodes prepared in examples 1 to 3 are suitable for use in EIGA processes.
Example 4
This embodiment differs from embodiment 1 in that:
in step S6, performing hot isostatic pressing treatment on the bar obtained in step S5: firstly, degassing the bar stock obtained in the step S5 by adopting a sheath, wherein the degassing temperature is kept at 300 ℃, and the vacuum degree is 10 in the degassing process -3 And judging that the degassing is finished when Pa is not changed, then clamping a branch exhaust pipeline for hot isostatic pressing, controlling the temperature at 1000 ℃, controlling the pressure at 150Mpa and the pressure maintaining time at 1h, and obtaining the high-purity electrode blank for the spherical copper-chromium alloy powder process.
Example 5
This embodiment differs from embodiment 4 in that:
in step S6, performing hot isostatic pressing treatment on the bar obtained in step S5: firstly, degassing the bar stock obtained in the step S5 by adopting a sheath, wherein the degassing temperature is kept at 500 ℃, and the vacuum degree is 10 in the degassing process -3 And judging that the degassing is finished when Pa is not changed, then clamping a branch exhaust pipeline for hot isostatic pressing, controlling the temperature at 1020 ℃, controlling the pressure at 250Mpa and the pressure maintaining time at 2 hours to obtain the high-purity electrode blank for the spherical copper-chromium alloy powder process.
Example 6
This embodiment differs from embodiment 4 in that:
in step S6, performing hot isostatic pressing treatment on the bar obtained in step S5: firstly, degassing the bar stock obtained in the step S5 by adopting a sheath, wherein the degassing temperature is kept at 600 ℃, and the vacuum degree is 10 in the degassing process -3 And judging that the degassing is finished when Pa is not changed, then clamping a branch exhaust pipeline for hot isostatic pressing, controlling the temperature at 1050 ℃, controlling the pressure at 350Mpa, and maintaining the pressure for 3 hours to obtain the high-purity electrode blank for the spherical copper-chromium alloy powder process.
The electrodes prepared in examples 4 to 6 are suitable for the PREP process.
The electrode material properties of examples 1 to 6 were measured, and the measurement results are shown in Table 1.
Table 1 electrode material property test results of examples 1 to 6 and blank
It can be seen from table 1 that the gas contents of examples 2 and 5 are far lower than the control (smelting) process, mainly due to the earlier degassing of chromium, and that examples 2 and 5 do not use crucible smelting, so that there is no crucible gassing, and that the gas content of example 5 is lower, mainly due to the better degassing of the hot isostatic pressing process.
From the data, it can be seen that the impurity content of examples 2 and 5 is lower than that of the control (smelting method) process, especially the silicon, calcium and magnesium content is obviously reduced, and this is mainly that the control smelting method needs a crucible as a carrier, and the crucible falls off in the process, so that impurities are introduced. The reason why the silicon aluminum of examples 2 and 5 is low is volatilization.
From the data, the density of the examples 1-3 is more than 85%, the EIGA process is satisfied, the density of the examples 4-6 is more than 98%, and the strength requirement of the PREP pulverizing process is satisfied.
Claims (9)
1. The preparation method of the high-purity electrode for the spherical copper-chromium alloy powder process is characterized by comprising the following steps of:
s1, compounding carbon:
taking chromium powder, detecting the oxygen content of the chromium powder, carrying out carbon matching according to the oxygen content of the chromium powder, and carrying out carbon matching according to a reaction equation of thermal carbon reduction to obtain O: c is calculated according to the molar ratio of 1:1 to obtain a carbon proportioning ratio A, the adding amount of carbon powder is added according to 50% -80% of the ratio A to ensure that the carbon powder is in an under-carbon state, then the chromium powder and the carbon powder are mixed manually, the powder is mixed for 1-3 hours by using a mixer, finally the carbon powder and the chromium powder collide with each other by using an air flow mill to uniformly adhere to the surface of the chromium powder, then the adding ratio B of carbon in the chromium powder is detected by sampling, the carbon powder (A-B) multiplied by 1.05 is supplemented, and after the mixture is mixed uniformly by hand, the mixture is mixed uniformly according to the following conditions: copper ball = 100: ball milling and powder mixing are carried out for 3-10 h according to the weight proportion of 100;
s2, sintering and degassing:
loosely filling the uniformly mixed chromium powder in the S1, pouring the uniformly mixed chromium powder into a graphite crucible, and then placing the graphite crucible into a vacuum sintering furnace for vacuum sintering and degassing to obtain a chromium powder blank;
s3, crushing and pulverizing:
crushing and pulverizing the chromium powder blank subjected to sintering and degassing in the step S2 to obtain high-purity low-gas chromium powder with the particle size of 450-830 mu m;
s4, mixing copper and chromium:
proportioning and mixing the oxygen-free copper powder and the high-purity low-gas chromium powder obtained in the step S3 according to a required proportion to obtain mixed powder A, and adding the third elements such as Zr, te and the like according to the required proportion if the electrode material is required to be added, wherein the mixed powder A is prepared by the following steps: copper ball = 100: ball milling and mixing powder for 3-12 h according to the weight ratio of 100 to obtain mixed powder B;
s5, cold isostatic pressing:
pressing the mixed powder B obtained in the step S4 in a cold isostatic pressing mode to obtain a bar stock;
s6, bar alloying:
carrying out alloying treatment on the bar stock obtained in the step S5 to obtain a high-purity electrode blank for the spherical copper-chromium alloy powder process;
s7, machining:
and (3) processing the electrode material blank prepared in the step (S6) into a required size according to the drawing requirement, and obtaining the high-purity electrode for the spherical copper-chromium alloy powder process.
2. The method for preparing the high-purity electrode for the spherical copper-chromium alloy powder process according to claim 1, wherein the particle size of the carbon powder is 1-6.5 μm.
3. The method for preparing a high purity electrode for spherical copper chromium alloy powder process according to claim 1, wherein the vacuum sintering and degassing method in step S2 is as follows: vacuumizing until the vacuum degree in the sintering furnace is below 1Pa, raising the temperature in the vacuum sintering furnace to 300-600 ℃ at a heating rate of 3-5 ℃/min, preserving heat for 20-40 min, so that the gas adsorbed on the surface of the chromium powder is pumped away, raising the temperature in the vacuum sintering furnace to 1400-1500 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 4-8 h.
4. The method for preparing a high purity electrode for a spherical copper-chromium alloy powder process according to claim 1, wherein the method for crushing and pulverizing in step S3 is as follows: crushing by a jaw crusher, and grinding by a vibration mill or an air flow mill.
5. The method for preparing the high-purity electrode for the spherical copper-chromium alloy powder process according to claim 1, wherein in the step S4, the ratio of the oxygen-free copper powder to the high-purity low-gas-chromium powder is as follows: cu: cr=99.9: 0.1 to 30:70.
6. the method for preparing the high-purity electrode for the spherical copper-chromium alloy powder process according to claim 1, wherein in the step S5, the cold isostatic pressing is dry-bag type cold isostatic pressing, the pressure of the cold isostatic pressing is controlled to be 100-280 Mpa, and the pressure maintaining time is 3-15 min.
7. The method for preparing a high purity electrode for a spherical copper chromium alloy powder process according to claim 1, wherein in step S6, the bar alloying treatment is a low temperature sintering treatment or a hot isostatic pressing treatment.
8. The method for preparing the high-purity electrode for the spherical copper-chromium alloy powder process according to claim 7, wherein the low-temperature sintering treatment method is as follows: putting the bar stock obtained in the step S5 into a vacuum sintering furnace, wherein the vacuum reaches 8 multiplied by 10 -1 The pa grade is lower, degassing is firstly carried out at 300-600 ℃, then inert gases such as argon and the like are filled to slight negative pressure, and the temperature is 980-1050 DEG CPreserving heat for 2-5 h.
9. The method for preparing the high-purity electrode for the spherical copper-chromium alloy powder process according to claim 7, wherein the hot isostatic pressing treatment is as follows: firstly, degassing the bar stock obtained in the step S5 by adopting a sheath, wherein the degassing temperature is kept between 300 and 600 ℃, and the vacuum degree is kept to 10 in the degassing process -3 And judging that the degassing is finished when Pa is not changed, then performing hot isostatic pressing, controlling the temperature to be 1000-1050 ℃, controlling the pressure to be 150-350 Mpa, and maintaining the pressure for 1-3 h.
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