CN113445046B - Tungsten alloy and method for laser cladding of tungsten alloy on surface of mold sprue cup - Google Patents
Tungsten alloy and method for laser cladding of tungsten alloy on surface of mold sprue cup Download PDFInfo
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- CN113445046B CN113445046B CN202110734857.6A CN202110734857A CN113445046B CN 113445046 B CN113445046 B CN 113445046B CN 202110734857 A CN202110734857 A CN 202110734857A CN 113445046 B CN113445046 B CN 113445046B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The tungsten alloy comprises the following components in parts by weight: 85-93 parts of tungsten, 7-9 parts of chromium, 0.5-1.5 parts of yttrium, 0.7-2 parts of zirconium hydride and 2-4 parts of lanthanum. The invention has the following advantages: the corrosion resistance can be further improved, the service life is prolonged, and the problem that the defects such as cracks and holes are easy to generate in the tungsten alloy laser cladding process is solved.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a tungsten alloy and a laser cladding method.
Background
The common manufacturing materials of the low-pressure casting die pouring cup are H13 and SKD61 high-performance hot-work die steel, the pouring cup made of the two materials is easy to corrode due to long-time direct contact with aluminum liquid during low-pressure casting of aluminum alloy, the time consumed for repair welding and repair of the corroded pouring cup is long, and when the pouring cup subjected to repair welding correction is used again, the corrosion speed of a repair welding part is accelerated, and the service life of the pouring cup can be greatly shortened. In addition, the inner wall of the sprue cup is easy to be adhered with aluminum, and the aluminum liquid filling is influenced by more aluminum adhesion, so that the internal structure of the product is loose, and the product is leaked and scrapped.
In the prior art, a pouring cup is generally subjected to nitriding treatment, namely the surface strength of the pouring cup is improved, the corrosion resistance is improved, and the sticking of a die is reduced by adjusting the depth of a nitriding layer and the nitriding hardness of the pouring cup, so that the service life of the pouring cup is prolonged, but the service life of the pouring cup is not obviously prolonged by the nitriding treatment, and is about 3500 die times; in order to prolong the service life of the sprue cup, the sprue cup integrally prepared from the tungsten alloy appears in the prior art, and the tungsten alloy has the characteristics of ultrahigh heat conduction performance, thermal shock resistance, low thermal expansion coefficient under a high-temperature condition, no oxidation within 700 ℃ and no aluminum adhesion within 600 ℃, so that the service life of the sprue cup prepared from the tungsten alloy can be greatly prolonged, the die adhesion phenomenon is reduced, the maintenance cost is reduced, however, the tungsten alloy is expensive, and the manufacturing cost is higher.
In the prior art, an alloy is laser-clad on the surface of a mould to improve the corrosion resistance of a pouring cup, and the alloy has the corrosion resistance mainly because tungsten carbide with higher hardness and corrosion resistance is added, but the improvement of the corrosion resistance of the pouring cup by utilizing the higher hardness and corrosion resistance of the tungsten carbide has the following defects: in the alloy containing tungsten carbide, the proportion of tungsten carbide is less, and can only account for 10-30%, and the less proportion of tungsten carbide means that the corrosion resistance of the alloy is not too high; if too much tungsten carbide is added to improve the corrosion resistance of the alloy, cracks, holes and other defects are easily generated in the alloy laser cladding process.
In the prior art, tungsten-nickel alloy only containing tungsten and nickel is prepared to improve the corrosion resistance of the sprue cup, but the metal powder has poor ductility, low mechanical strength, higher melting point, difficult laser cladding and poor cladding effect.
In addition, CN201910703560.6 also discloses a metal laser cladding printed two-dimensional collimator material and a preparation method thereof, wherein the metal laser cladding printed two-dimensional collimator material includes: a metal powder. Preferably, the metal powder is tungsten or molybdenum alloy powder or is a uniformly mixed powder of tungsten or molybdenum and other low-melting point metal, such as WxCu 1 -x alloys with a copper content of 5% to 50%; WxNi 1 -x-yFey，WxNi 1 -x-yCuy，WxNi 1 -x-yCry, wherein x + y =5% -50%, which component is useful for molybdenum alloys. Preferably, the metal powder is a uniformly mixed powder of tungsten or molybdenum and other low-melting-point elemental metals, such as WxNi1-x-yFey, WxNi 1 -x-yCuy，WxNi 1 -x-yCry, wherein x + y =5% -50%, which component is useful for molybdenum alloys. Preferably, the tungsten or molybdenum alloy powder may be a quaternary alloy, such as WxCu 1 -x-y-zNiyFeZ、WxCu 1 -x-y-zNiyCrZ、WxCu 1 -x-y-zNiyZnZ、WxCu 1 -x-y-zNiyTiZ, wherein x + y + z =5% -10%, which component can be used for molybdenum alloys.
In the metal laser cladding printing two-dimensional collimator material, although the metal powder is tungsten or molybdenum alloy powder or even mixed powder of tungsten or molybdenum and other low-melting-point metals, the maximum content of tungsten or molybdenum in the tungsten or molybdenum alloy powder is only 45% according to the content of the alloy, and the rest is low-melting-point simple substance metal, so that the defects of poor mechanical strength, high melting point and poor metal forming capability can be solved, but the corrosion resistance is still poor.
Disclosure of Invention
The invention aims to provide a tungsten alloy which can further improve the corrosion resistance and prolong the service life and solve the problem that cracks, holes and other defects are easy to generate in a tungsten alloy laser cladding process.
The invention also aims to provide a method for laser cladding of tungsten alloy on the surface of the die pouring cup, which is used for laser cladding of tungsten alloy on the pouring cup, so that the service life of the pouring cup is greatly prolonged.
The invention aims to realize that the tungsten alloy comprises the following components in parts by weight: 85-93 parts of tungsten, 7-9 parts of chromium, 0.5-1.5 parts of yttrium, 0.7-2 parts of zirconium hydride and 2-4 parts of lanthanum.
In the invention, the working principle is as follows: tungsten has ultrahigh heat-conducting property and thermal shock resistance, and has better high-temperature hardness and higher aluminum liquid corrosive wear resistance; 7-9 parts of chromium promotes the generation of a compact oxide film, and the high-temperature corrosion resistance of the alloy is improved; zirconium hydride ZrH 2 In the laser cladding process, the tungsten alloy can be decomposed to provide zirconium Zr atoms, and the zirconium Zr and yttrium Y have combined action, so that the toughness of the tungsten alloy is improved, the brittleness of a compact oxide film is reduced, and the binding force between the oxide film and a sprue cup substrate is improved, so that the compact oxide film with a protection effect cannot fall off in a thermal shock process, and the service life of the tungsten alloy on the sprue cup substrate is prolonged; the lanthanum La of 2-4 parts can reduce the defects in the laser cladding tungsten alloy coating and improve the density of the tungsten alloy coating. Since pure Zr is easily oxidized, pure Zr cannot be used in the tungsten alloy to replace zirconium hydride ZrH 2 。
The coating prepared from the tungsten alloy has the characteristics of ultrahigh heat-conducting property, better high-temperature hardness, higher aluminum liquid corrosion and abrasion resistance and no aluminum sticking, and can greatly prolong the service life of the tungsten alloy, thereby prolonging the service life of a matrix; the high strength and toughness of the coating prepared from the tungsten alloy can greatly improve the thermal shock resistance of the coating, improve the binding force between the tungsten alloy coating and the sprue cup substrate, and prevent the tungsten alloy coating from falling off from the sprue cup substrate, so that the time of the tungsten alloy coating on the sprue cup substrate is prolonged, and the service life of the substrate is prolonged.
In addition, the coating prepared from the tungsten alloy has no cracks and a compact tissue structure, the density of the coating reaches more than 99%, the content of tungsten is high, even if the content of tungsten is more than 90%, the defects of cracks, holes and the like of the tungsten alloy in a laser cladding process can not be caused, the corrosion resistance of the tungsten alloy is further greatly improved, and the service life of the tungsten alloy is further prolonged.
In addition, because the tungsten has a high melting point and is not easy to adhere, the chromium, the yttrium, the zirconium hydride and the lanthanum which have low melting points are beneficial to the adhesion among elements, and the mechanical strength of the tungsten alloy and the forming capability of a coating are improved. The heat-conducting property, the high-temperature hardness and the aluminum liquid corrosion and abrasion resistance of the tungsten alloy can be reduced due to less tungsten content; when the tungsten content is high, other powder is less, so that the elements are not easy to adhere, the coating has defects of cracks, holes and the like, and the density, the toughness, the thermal shock resistance, the service life and the like of the tungsten alloy coating are influenced. Under the conditions of 85-93 parts of tungsten, 7-9 parts of chromium, 0.5-1.5 parts of yttrium, 0.7-2 parts of zirconium hydride and 2-4 parts of lanthanum, the corrosion resistance can be improved, the service life can be prolonged, and the problem that the defects such as cracks, holes and the like are easy to generate in the tungsten alloy laser cladding process can be solved.
Further, the paint comprises the following components in parts by weight: 90-93 parts of tungsten, 7.8-8 parts of chromium, 0.9-1.2 parts of yttrium, 1.5-1.8 parts of zirconium hydride and 2.6-3.5 parts of lanthanum. The components in the proportion can further greatly improve the corrosion resistance of the coating, prolong the service life of the coating, and solve the problem of easy generation of cracks, holes and other defects in the tungsten alloy laser cladding process while basically combining the corrosion resistance with the basic combining force.
Further, tungsten, chromium, yttrium, zirconium hydride and lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 20um-70 um. The purities of tungsten, chromium, yttrium, zirconium hydride and lanthanum are more than 98 percent, so that the problems that unexpected phases or inclusions are generated in the laser cladding process, and the corrosion resistance, the compactness, the toughness, the thermal shock resistance, the service life and the like are influenced are solved; the reason why the average particle size is set to 20um to 70um is that in the laser cladding process, the average particle size is too small, the powder has poor flowability, the powder feeding pipe may be blocked, and the particle size is too large, so that the powder cannot be melted by laser energy, or a large laser power density is required for melting.
The invention also aims to realize the method for laser cladding of the tungsten alloy on the surface of the die sprue cup, which comprises the following steps:
weighing the tungsten alloy;
mixing tungsten alloy, ball milling and drying;
cleaning the surface of the pouring cup, and removing oxide skin on the surface;
and carrying out laser cladding on the dried tungsten alloy on the surface of the sprue cup under the protection of inert gas.
The working principle is as follows: the tungsten alloy is cladded on the surface of the H13 and SKD61 die sprue cup by a laser cladding method to form a tungsten alloy coating, the tungsten alloy coating is metallurgically bonded with the matrix sprue cup, the tungsten alloy coating has no cracks and is compact in tissue structure, the coating density is close to 100%, the tungsten alloy coating has the characteristics of strong wear resistance, high corrosion resistance and no aluminum adhesion, the aluminum die adhesion phenomenon is reduced, the service life of the tungsten alloy coating is greatly prolonged, the bonding force of the tungsten alloy and the sprue cup matrix is improved, and the tungsten alloy is prevented from falling off from the matrix, so that the service life of the sprue cup is further greatly prolonged, and the maintenance cost is reduced.
Further, the laser cladding process parameters include: the diameter of a light spot is 3mm-4mm, the laser power is 4kw-6kw, and the cladding speed is 7mm/s-11 mm/s. The technological parameters of laser cladding have great influence on the dilution rate, cracks, surface roughness, compactness and the like of the cladding layer; the larger the laser power is, the more the melted cladding metal quantity is, and the larger the probability of generating the air holes is. Along with the increase of the laser power, the depth of the cladding layer is increased, the surrounding liquid metal is fluctuated violently, and the liquid metal is solidified and crystallized dynamically, so that the number of air holes is gradually reduced and even eliminated, and the cracks are also gradually reduced. When the depth of the cladding layer reaches the limit depth, the surface temperature of the substrate rises along with the increase of the power, the phenomena of deformation and cracking are aggravated, the laser power is too low, only the surface coating melts, the substrate does not melt, and at the moment, local balling, cavities and the like appear on the surface of the cladding layer, so that the purpose of surface cladding cannot be achieved. Under the condition of certain laser power, the dilution rate of the cladding layer is reduced along with the increase of the diameter of the light spot, and when the cladding speed and the diameter of the light spot are fixed, the dilution rate of the cladding layer is increased along with the increase of the laser beam power. The cladding speed is too high, the alloy powder can not be completely melted, and the effect of high-quality cladding is not achieved; the cladding speed is too low, the existing time of a molten pool is too long, powder is over-sintered, alloy elements are lost, and meanwhile, the heat input quantity of a matrix is large, so that the deformation quantity can be increased. Considering that the base body of the invention is the H13 and SKD61 die pouring cup, the cladding layer is the tungsten alloy, and the laser cladding parameters do not influence the macroscopic quality and the microscopic quality of the cladding layer independently, but influence each other, and are a very complicated process, the base body material, the tungsten alloy material and the laser cladding parameters have a synergistic effect, the invention finally sets the spot diameter to be 3mm-4mm, the laser power to be 4kw-6kw, and the cladding speed to be 7mm/s-11 mm/s.
Further, the laser cladding process parameters further include: the multi-pass lapping rate is 40-60%, and the powder feeding rate is 9 g/min. In multi-channel laser cladding, the lapping rate is a main factor influencing the surface roughness of a cladding layer, the lapping rate is improved, the surface roughness of the cladding layer is reduced, but the uniformity of the lapping part is difficult to ensure. In order to ensure good evenness of the overlapping part while ensuring a cladding layer with good flatness, the multi-pass overlapping rate is set to be 40-60%. The powder feeding speed of 9g/min can improve the effective utilization rate of laser heat and the effective utilization rate of cladding materials to the maximum extent.
Further, the ball milling comprises vacuumizing a ball milling tank, introducing argon for protection, and adding alcohol for wet milling after powder dry milling. The argon is introduced, and the effects of dry grinding and wet grinding are to ensure the purity and the grain size of tungsten, chromium, yttrium, zirconium hydride and lanthanum in the tungsten alloy.
Further, the drying temperature was 180 ℃. The powder treated at a temperature higher than 180 ℃ is oxidized, and the drying efficiency of the powder is affected at a temperature lower than 180 ℃.
Further, the drying time was 8 h. Drying times longer than 8 hours are not only wasteful of time and energy, but also increase the oxygen content of the powder.
The increased powder oxidation/oxygen content reduces the ductility and impact toughness of the coating, thereby reducing the life of the tundish, and in addition, the increased oxidation/oxygen content also causes impurities from oxidized oxides during laser cladding, which affects the compactness and formability of the coating.
Compared with the prior art, the invention has the following beneficial effects:
1. the coating prepared by the tungsten alloy provided by the invention has no cracks and compact tissue structure, and the density of the coating reaches more than 99%.
2. The wear resistance is strong, the corrosion resistance is high, the aluminum die sticking phenomenon can be reduced, and the maintenance cost is reduced.
3. The production test shows that the service life of the sprue cup can be greatly prolonged by using the effect display.
Detailed Description
Example 1
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 85 parts of tungsten, 7 parts of chromium, 1.5 parts of yttrium, 2 parts of zirconium hydride and 4 parts of lanthanum. Mixing the powder, performing ball milling, vacuumizing a ball milling tank, introducing argon for protection, performing dry milling on the powder for 9 hours, adding alcohol, performing wet milling for 2 hours, and drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 20 percent.
The method for laser cladding of tungsten alloy on the surface of the mold sprue cup comprises the following steps
The laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4.2kw, the cladding speed is 8mm/s, the multi-channel lap joint rate is 45%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the pouring cup, removing oxide skin on the surface, and ultrasonically cleaning the pouring cup by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.5%. The service life of the pouring cup of the embodiment is 9800 times of die by production inspection.
Example 2
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 85 parts of tungsten, 9 parts of chromium, 1.5 parts of yttrium, 2 parts of zirconium hydride and 4 parts of lanthanum. Mixing the powder, ball milling, vacuumizing a ball milling tank, introducing argon for protection, carrying out dry milling on the powder for 9 hours, adding alcohol, carrying out wet milling for 2 hours, and then drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 70 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4.2kw, the cladding speed is 8mm/s, the multi-channel lap joint rate is 45%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the sprue cup, removing oxide skin on the surface, and ultrasonically cleaning by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.6%. The service life of the pouring cup of the embodiment is 9500 times of a die by production inspection.
Example 3
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 85 parts of tungsten, 9 parts of chromium, 1.5 parts of yttrium, 1 part of zirconium hydride and 3 parts of lanthanum. Mixing the powder, ball milling, vacuumizing a ball milling tank, introducing argon for protection, carrying out dry milling on the powder for 9 hours, adding alcohol, carrying out wet milling for 2 hours, and then drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 70 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4.2kw, the cladding speed is 8mm/s, the multi-channel lap joint rate is 45%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the sprue cup, removing oxide skin on the surface, and ultrasonically cleaning by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.5%. The service life of the pouring cup of the embodiment is 9700 times by production inspection.
Example 4
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 85 parts of tungsten, 10 parts of chromium, 1.5 parts of yttrium, 2 parts of zirconium hydride and 5 parts of lanthanum. Mixing the powder, performing ball milling, vacuumizing a ball milling tank, introducing argon for protection, performing dry milling on the powder for 9 hours, adding alcohol, performing wet milling for 2 hours, and drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 70 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4.2kw, the cladding speed is 8mm/s, the multi-channel lapping rate is 45%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the pouring cup, removing oxide skin on the surface, and ultrasonically cleaning the pouring cup by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.7%. The service life of the pouring cup of the embodiment is 8900 die times through production inspection.
Example 5
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 85 parts of tungsten, 3 parts of chromium, 1.5 parts of yttrium, 2 parts of zirconium hydride and 1 part of lanthanum. Mixing the powder, ball milling, vacuumizing a ball milling tank, introducing argon for protection, carrying out dry milling on the powder for 9 hours, adding alcohol, carrying out wet milling for 2 hours, and then drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 70 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 sprue cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4.2kw, the cladding speed is 8mm/s, the multi-channel lap joint rate is 45%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the pouring cup, removing oxide skin on the surface, and ultrasonically cleaning the pouring cup by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and is compact in tissue structure, and the compactness of the coating is 99.1%. The service life of the pouring cup of the embodiment is 9500 times of a die by production inspection.
Example 6
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 93 parts of tungsten, 7 parts of chromium, 0.5 part of yttrium, 0.7 part of zirconium hydride and 2 parts of lanthanum. Mixing the powder, performing ball milling, vacuumizing a ball milling tank, introducing argon for protection, performing dry milling on the powder for 9 hours, adding alcohol, performing wet milling for 2 hours, and drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 50 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 3mm, the laser power is 4kw, the cladding speed is 7mm/s, the multi-channel lap joint rate is 40%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the pouring cup, removing oxide skin on the surface, and ultrasonically cleaning the pouring cup by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.6%. The service life of the pouring cup of the embodiment is 10100 times by production inspection.
Example 7
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 90 parts of tungsten, 8 parts of chromium, 1.1 parts of yttrium, 1.2 parts of zirconium hydride and 3 parts of lanthanum. Mixing the powder, ball milling, vacuumizing a ball milling tank, introducing argon for protection, carrying out dry milling on the powder for 9 hours, adding alcohol, carrying out wet milling for 2 hours, and then drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 50 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 4mm, the laser power is 5.8kw, the cladding speed is 10mm/s, the multi-channel lap joint rate is 43%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the pouring cup, removing oxide skin on the surface, and ultrasonically cleaning the pouring cup by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 99.7%. The service life of the pouring cup of the embodiment is 10300 times by production inspection.
Example 8
Weighing powder by using balance, wherein the powder comprises the following components in parts by weight: 90 parts of tungsten, 8 parts of chromium, 1.1 parts of yttrium, 1.2 parts of zirconium hydride and 3 parts of lanthanum. Mixing the powder, ball milling, vacuumizing a ball milling tank, introducing argon for protection, carrying out dry milling on the powder for 9 hours, adding alcohol, carrying out wet milling for 2 hours, and then drying at 180 ℃ for 8 hours. The tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 50 um.
The method for laser cladding of the tungsten alloy on the surface of the H13 pouring cup comprises the following steps:
the laser cladding process parameters are as follows: the diameter of a light spot is 4mm, the laser power is 8kw, the cladding speed is 10mm/s, the multi-channel lap joint rate is 43%, and the powder feeding rate is 9 g/min;
before laser cladding, cleaning the surface of the sprue cup, removing oxide skin on the surface, and ultrasonically cleaning by using absolute ethyl alcohol;
carrying out laser cladding under the protection of high-purity argon.
The alloying coating after the treatment of the embodiment is metallurgically bonded with the base body pouring cup, the alloying coating has no cracks and compact tissue structure, and the density of the coating is 98.4%. The service life of the pouring cup of the embodiment is 9500 times of a die by production inspection.
In the present invention, the powder was dry-milled for 9 hours and wet-milled with alcohol for 2 hours. Neither dry nor wet milling times can be too long or too short, too short mixing is not uniform, and too long wastes time and energy.
Example 2 compared with example 1, the difference is that the amount of chromium is different, and other conditions are the same. And observing whether cracks and holes are generated on the surface of the cladding coating.
Example 3 compared with example 1, the proportions of tungsten and yttrium were the same in example 3 and example 1, respectively, except that the proportions of chromium, zirconium hydride and lanthanum were changed, and the other conditions were the same. And observing whether cracks and holes are generated on the surface of the cladding coating.
In example 4, 10 parts of chromium and 5 parts of lanthanum were used as compared with example 1, and the other conditions were the same. And observing whether cracks and holes are generated on the surface of the cladding coating.
In example 5, 3 parts of chromium and 1 part of lanthanum were used as compared with example 1, and the other conditions were the same. And observing whether cracks and holes are generated on the surface of the cladding coating.
In example 8, the laser power was 8kw, as compared with example 7, and the other conditions were the same. And observing whether cracks and holes are generated on the surface of the cladding coating.
The density and service life of the cladding coating of the sample and the cracks and holes generated are detected, and the results are shown in table 1.
Table 1 cladding coating density, service life and cracks and holes generated for the samples treated in each example.
In example 4, compared with example 1, after excessive chromium and lanthanum are added, although cracks and holes are avoided, the tungsten content is directly reduced, which leads to the reduction of the corrosion resistance of the cladding coating and thus the reduction of the service life. In example 5, compared with example 1, by adding too little chromium and lanthanum, cracks are generated in the cladding coating after laser cladding, and the quality of the cladding layer is influenced. Comparing example 6 with example 7, the laser power in example 8 is too high, and after laser cladding, cracks and holes are directly generated on the cladding coating, which affects the quality of the cladding coating.
Claims (6)
1. A method for laser cladding of tungsten alloy on the surface of a mold sprue cup is characterized by comprising the following steps: the method comprises the following steps:
weighing a tungsten alloy, wherein the tungsten alloy consists of the following components in parts by weight: 85-93 parts of tungsten, 7-9 parts of chromium, 0.5-1.5 parts of yttrium, 0.7-2 parts of zirconium hydride and 2-4 parts of lanthanum;
mixing tungsten alloy, ball milling and drying;
cleaning the surface of the pouring cup, and removing oxide skin on the surface;
under the protection of inert gas, carrying out laser cladding on the dried tungsten alloy on the surface of the pouring cup, wherein,
the laser cladding process parameters comprise: the diameter of a light spot is 3mm-4mm, the laser power is 4kW-6kW, the cladding speed is 7mm/s-11mm/s, the multi-channel lap joint rate is 40% -60%, and the powder feeding rate is 9 g/min.
2. The method for laser cladding of tungsten alloy on the surface of the die sprue cup according to claim 1, wherein the method comprises the following steps: the composition comprises the following components in parts by weight: 90-93 parts of tungsten, 7.8-8 parts of chromium, 0.9-1.2 parts of yttrium, 1.5-1.8 parts of zirconium hydride and 2.6-3.5 parts of lanthanum.
3. The method for laser cladding of tungsten alloy on the surface of the mold sprue cup according to claim 1 or 2, wherein the method comprises the following steps: the tungsten, the chromium, the yttrium, the zirconium hydride and the lanthanum are respectively powder with the purity of more than 98 percent and the average grain diameter of 20um-70 um.
4. The method for laser cladding of tungsten alloy on the surface of the mold sprue cup according to claim 1 or 2, wherein the method comprises the following steps: the ball milling comprises vacuumizing a ball milling tank, introducing argon for protection, dry milling the powder, and then adding alcohol for wet milling.
5. The method for laser cladding of tungsten alloy on the surface of the die sprue cup according to claim 1 or 2, wherein the method comprises the following steps: the drying temperature was 180 ℃.
6. The method for laser cladding of tungsten alloy on the surface of the die sprue cup according to claim 5, wherein the method comprises the following steps: the drying time was 8 h.
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