CN101575690B - Preparation method for fine crystalline refractory metal - Google Patents

Preparation method for fine crystalline refractory metal Download PDF

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Publication number
CN101575690B
CN101575690B CN2009103034780A CN200910303478A CN101575690B CN 101575690 B CN101575690 B CN 101575690B CN 2009103034780 A CN2009103034780 A CN 2009103034780A CN 200910303478 A CN200910303478 A CN 200910303478A CN 101575690 B CN101575690 B CN 101575690B
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refractory metal
metal material
laser
scanning
laser apparatus
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CN101575690A (en
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都业志
侯进
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BAOJI YUNJIE METAL PRODUCTS Co Ltd
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BAOJI YUNJIE METAL PRODUCTS Co Ltd
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Abstract

A preparation method for fine crystalline refractory metal comprises the steps as follows: preparing a refractory metal by the prior powder metallurgy or plasma spraying, and then scanning the refractory metal block with laser beams of certain power at a certain speed, melting and solidifying the material quickly, thereafter, placing the refractory metal under vacuum or in the atmosphere of hydrogen gas after the material is scanned by the laser, keeping the temperature at 1150-1500 DEG C for 30-60min, and annealing, to obtain the refractory metal with thinned crystal grains. The fine crystalline refractory metal obtained by the method in the invention removes the residual pores in the material so that the material density, particularly the distribution homogeneity of alloy elements is increased, thereby improving all performances of the material.

Description

A kind of preparation method of fine crystalline refractory metal
Technical field
The invention belongs to technical field of material, relate to a kind of preparation method of fine crystalline refractory metal.
Background technology
Tantalum in the refractory metal, niobium and alloy thereof, usually adopt electron beam or electric arc furnace that metallic substance is melted and make bar-shaped blank, after then should bar-shaped blank heating, adopt extruding, forging and method such as rolling to make the block materials of various plates, rod, band or different shape such as thin; Simultaneously, the tantalum niobium of melting is slowly cooling under melting state, and the material grains that obtains is thick, though adopt large extrusion ratio to push the refinement that can realize crystal grain, is difficult to obtain the ultra-fine equiax crystal of uniform crystal particles.Tungsten that fusing point is higher and molybdenum generally adopt the powder metallurgic method preparation, at first metal-powder are pressed into blank, then this blank are carried out vacuum or hydrogen atmosphere sintering, form the fine and close relatively block materials that can process.Adopt powder metallurgic method to prepare the tungsten metallic substance, its solid state sintering mode itself has determined that material has residual porosity, and the grain size inequality, and for miramint, machinery or chemical powdering method all can't realize the homogeneity of material composition.And composition is uneven and residual porosity causes mechanical property, electrical property and the electron emission capability of material to reduce.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of fine crystalline refractory metal can not only guarantee mechanical property, electrical property and the electron emission capability of refractory metal, and the refractory metal material composition that makes is even, organizes tiny even, the no residual porosity of crystal grain.
The technical solution adopted in the present invention is, a kind of preparation method of fine crystalline refractory metal, adopt existing powder metallurgy or plasma spraying method to make refractory metal material, then the laser beam of this refractory metal block materials with certain power and speed scanned, material is melted and rapid solidification fast, afterwards, refractory metal material after the laser scanning is carried out anneal in vacuum or hydrogen atmosphere, eliminate stress, obtain the material of super-refinement crystal grain, eliminate the sintering hole, improve the density of material, especially improve the homogeneity that alloy element distributes, thereby improve the every performance of material, this method is carried out according to the following steps:
Step 1: adopt existing powder metallurgy or plasma spraying method to make refractory metal material;
Step 2: adopt laser apparatus that the refractory metal material that step 1 makes is scanned, this refractory metal material is melted, then rapid solidification in the laser beam flying zone;
Step 3: the refractory metal material of step 2 after laser scanning placed vacuum or hydrogen atmosphere, be under 1150~1500 ℃ the condition in temperature, insulation 30min~60min carries out anneal, makes the refractory metal material of grain ultrafining, no residual porosity.
Wherein, the laser apparatus in the step 2 adopts solid statelaser or CO 2Laser apparatus.
Wherein, in the scanning process of step 2,
Needing the refractory metal material of scanning is molybdenum and molybdenum alloy, and the output rating of control laser apparatus is 1KW~3KW, and scanning speed is 25mm/min~70mm/min, and the spot diameter of laser beam is 1.0mm~1.5mm,
Needing the refractory metal material of scanning is tungsten and tungstenalloy, and the output rating of control laser apparatus is 1.5KW~3KW, and scanning speed is 25mm/min~70mm/min, and the spot diameter of laser beam is 1.0mm~1.5mm.
Preparation method of the present invention adopts the laser of certain power and speed refractory metal material to be carried out the scanning irradiation of certain depth, make no residual porosity in the refinement of crystal grain height, homogeneous microstructure, material of refractory metal material, obtain near or obtain the uniform refractory metal material of composition of theoretical density, guaranteed mechanical property, electrical property and the electron emission capability of material.For alloy, alloying elements distribution is even.
Description of drawings
Fig. 1 is the metallographic microstructure figure that adopts a kind of alloy that existing method makes;
Fig. 2 is that alloy material shown in Figure 1 adopts the metallographic microstructure figure after the inventive method is handled.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments.
Usually adopt and forge or working method such as rolling improves the density of material, and the density of the material that these methods make is relatively poor, also has hole, and material cost sharply raises, the utilization ratio of material is lower.For example for the molybdenum electrode of glass or refractory fibre fusing usefulness, the erosion rate that the hole that the surface exists can aggravate melt counter electrode material, the work-ing life of reducing electrode.For electronics or gamma ray emission material, the density of material and homogeneity of structure are the keys of decision material electronics emittance and quantity of X-rays X.
In fixed anode X-x ray tube, fine and close tungsten metal produces ray as anode under electron-bombardment.Tungsten anodic traditional preparation process method is, prepares sintered tungsten bar with powder metallurgic method earlier, and tungsten bar is being not less than under 1500 ℃ of temperature insulation and forging repeatedly, to improve its density.Tungsten bar after the forging cuts into thin slice according to dimension line, and two-sided then plain grinding can be used for fixing pipe.This technical process is long, material use efficiency is on the low side.
The inventive method adopts existing powder metallurgy or plasma spraying method to make refractory metal material, then this refractory metal block materials is carried out the scanning of certain depth with the laser beam of certain power and speed, material is melted and rapid solidification fast, afterwards, refractory metal material after the laser scanning is carried out anneal in vacuum or hydrogen atmosphere, eliminate stress, obtain the material of super-refinement crystal grain, eliminate the sintering hole, improve the density of material, especially improve the homogeneity that alloy element distributes, thereby improve the every performance of material.This method is carried out according to the following steps:
Step 1: adopt existing powder metallurgy or plasma spraying method to make refractory metal material;
Step 2: adopt laser apparatus that the refractory metal material that step 1 makes is scanned, this refractory metal material is melted, then rapid solidification in the laser scanning zone;
Adopting solid statelaser or rated output is the CO of 5KW 2Laser apparatus, in the scanning process, the output rating of controlling this laser apparatus is 1KW~3KW, and scanning speed is 25mm/min~70mm/min, and spot diameter is 1.0mm~1.5mm.
The output rating of laser beam is different according to material character, and for molybdenum and molybdenum alloy, laser output power is not less than 1kw, and the laser output power of tungsten and tungstenalloy is not less than 1.5KW.
Step 3: the refractory metal material of step 2 after laser scanning placed vacuum or hydrogen atmosphere, is under 1150~1500 ℃ the condition in temperature, and insulation 30~60min carries out anneal, makes the refractory metal material of grain ultrafining, no residual porosity.
The unit energy density height of laser beam, the Heating temperature of laser beam up to 5000 ℃~10000 ℃.Laser beam irradiation melts metal moment to the metallic substance, and cooling rapidly, makes the metal melt rapid solidification, thereby realizes the densification and the grain refining of material.
Embodiment 1
Adopt plasma spraying method to obtain the pure tungsten coating that thickness is 1.0~1.5mm on steel matrix, the density of this coating is 17.86g/cm after testing 3(theoretical density 91.3%).Adopt the CO of rated output 5KW 2Laser apparatus carries out laser scanning to this pure tungsten coating and handles as laser source, and the output rating of laser apparatus is 1.5KW in the treating processes, scanning speed 25mm/min, spot diameter 1.0mm; Material after the laser scanning is placed vacuum environment, under 1150 ℃ temperature, be incubated 60min, obtain the pure tungsten coating of grain ultrafining, no residual porosity.The scan depths of this pure tungsten coating is 0.85~0.92mm after testing, and density is 19.2g/cm 3, not finding hole, dense structure is even.
Embodiment 2
Adopting powder metallurgic method to make the W-3Re alloy block, is under 1500 ℃ the condition, behind the heating 60min, to forge in temperature with this alloy block, and the deflection of thickness direction is 27%, makes metallography microscope W-Re alloys block materials as shown in Figure 1.The employing line cuts, and the W-Re alloys block materials that makes is cut into the square of 50 * 50mm; Then, adopt CO 2Laser apparatus carries out laser scanning to the square material that cuts and handles as laser source, and the output rating of laser apparatus is 3KW in the treating processes, and scanning speed is 48mm/min, and spot diameter is 1.5mm; Alloy material after the laser scanning is placed hydrogen atmosphere, under 1500 ℃ temperature, be incubated 30min, make the W-Re alloys block materials of grain ultrafining, no residual porosity.The scan depths of this alloy block material is 1.1mm after testing, its metallographic microstructure figure as shown in Figure 2, as can be seen from Figure, compared to Figure 1, the tiny even compact of crystal grain of the alloy material after laser scanning is handled, no residual porosity.
Embodiment 3
With purity be 99.95% tungsten powder by punching block compacting, sintering, making diameter is that 23mm, thickness are the thin cylinder of 2.2mm, detecting its density is 18.5g/cm 3Adopt solid statelaser that the one side that will approach cylinder is carried out laser scanning and handle, output power of laser is 2.5KW in the treating processes, and scanning speed is 70mm/min, and spot diameter is 1.25mm; Thin cylinder after the laser scanning is placed vacuum environment, and under 1325 ℃ temperature, insulation 45min makes the tungstenalloy thin column material that one side has grain ultrafining, no residual porosity.This tungstenalloy thin column material is carried out two-sided plain grinding, and the laser treatment face is used for fixing canal ray tube as the electron emission face, has not only reduced cost, and the controllability of technology and repeated owing to being guaranteed to be improved by program and equipment fully.
Embodiment 4
Adopting powder metallurgic method to make molybdenum TZM alloy block, is under 1500 ℃ the condition, behind the heating 60min, to forge in temperature with this molybdenum TZM alloy block, and the deflection of thickness direction is 27%, makes molybdenum TZM alloy block material.The employing line cuts, and the molybdenum TZM alloy block material that makes is cut into the square of 50 * 50mm; Then, adopt CO 2Laser apparatus carries out laser scanning to the square material that cuts and handles as laser source, and the output rating of laser apparatus is 1KW in the treating processes, and scanning speed is 25mm/min, and spot diameter is 1.0mm; Alloy material after the laser scanning is placed hydrogen atmosphere, under 1500 ℃ temperature, be incubated 30min, make the molybdenum TZM alloy block material of grain ultrafining, no residual porosity.The scan depths of this alloy block material is 1.3mm after testing.
Embodiment 5
Adopt plasma spraying method to obtain the pure molybdenum coating that thickness is 1.0~1.5mm on steel matrix, the density of this coating is 8.69g/cm after testing 3(theoretical density 91.95%).Adopt the CO of rated output 5KW 2Laser apparatus carries out laser scanning to this pure molybdenum coating and handles as laser source, and the output rating of laser apparatus is 3KW in the treating processes, scanning speed 70mm/min, spot diameter 1.5mm; Material after the laser scanning is placed vacuum environment, under 1150 ℃ temperature, be incubated 60min, obtain the pure molybdenum coating of grain ultrafining, no residual porosity.The scan depths of this pure molybdenum coating is 0.92~1.2mm after testing, and density is 9.2g/cm 3, not finding hole, dense structure is even.
Embodiment 6
With purity be 99.95% molybdenum powder by punching block compacting, sintering, making diameter is that 23mm, thickness are the thin cylinder of 2.2mm, detecting its density is 8.94g/cm 3Adopt solid statelaser that the one side that will approach cylinder is carried out laser scanning and handle, output power of laser is 2KW in the treating processes, and scanning speed is 50mm/min, and spot diameter is 1.25mm; Thin cylinder after the laser scanning is placed vacuum environment, and under 1325 ℃ temperature, insulation 45min makes the molybdenum alloy thin column material that one side has grain ultrafining, no residual porosity.This molybdenum alloy thin column material is carried out two-sided plain grinding, and the laser treatment face is used for fixing canal ray tube as the electron emission face, has not only reduced cost, and the controllability of technology and repeated owing to being guaranteed to be improved by program and equipment fully.
The inventive method can realize refractory metal grain refining, improve its dense structure's degree, be in crystal grain thinning, to improve the material composition homogeneity for alloy, and then improve the over-all properties of material.

Claims (2)

1. the preparation method of a fine crystalline refractory metal is characterized in that, this method is carried out according to the following steps:
Step 1: adopt existing powder metallurgy or plasma spraying method to make refractory metal material;
Step 2: adopt laser apparatus that the refractory metal material that step 1 makes is scanned, this refractory metal material is melted, then rapid solidification in the laser beam flying zone;
Needing the refractory metal material of scanning is molybdenum and molybdenum alloy, and the output rating of control laser apparatus is 1KW~3KW, and scanning speed is 25mm/min~70mm/min, and the spot diameter of laser beam is 1.0mm~1.5mm,
Needing the refractory metal material of scanning is tungsten and tungstenalloy, and the output rating of control laser apparatus is 1.5KW~3KW, and scanning speed is 25mm/min~70mm/min, and the spot diameter of laser beam is 1.0mm~1.5mm;
Step 3: the refractory metal material of step 2 after laser scanning placed vacuum or hydrogen atmosphere, be under 1150~1500 ℃ the condition in temperature, insulation 30min~60min carries out anneal, makes the refractory metal material of grain ultrafining, no residual porosity.
2. according to the described preparation method of claim 1, it is characterized in that the laser apparatus in the described step 2 adopts solid statelaser or CO 2Laser apparatus.
CN2009103034780A 2009-06-19 2009-06-19 Preparation method for fine crystalline refractory metal Expired - Fee Related CN101575690B (en)

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CN102260869B (en) * 2011-07-18 2012-12-26 北京科技大学 Method for preparing tungsten coating by using cold air dynamic spraying technology
CN104630682A (en) * 2015-01-23 2015-05-20 上海大学 Method for refining hot-dipping coating material by employing laser heat treatment

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