CN1314504C - Process of mfg. Mo alloyed targeting materials - Google Patents

Process of mfg. Mo alloyed targeting materials Download PDF

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CN1314504C
CN1314504C CNB2005100095854A CN200510009585A CN1314504C CN 1314504 C CN1314504 C CN 1314504C CN B2005100095854 A CNB2005100095854 A CN B2005100095854A CN 200510009585 A CN200510009585 A CN 200510009585A CN 1314504 C CN1314504 C CN 1314504C
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particle size
container
sintered body
average particle
powder
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CN1660526A (en
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岩崎克典
井上惠介
植村典夫
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Proterial Ltd
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Hitachi Metals Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/16—Both compacting and sintering in successive or repeated steps
    • B22F3/162—Machining, working after consolidation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/1208—Containers or coating used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Powder Metallurgy (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Disclosed is a method of producing a target material of a Mo alloy, which includes the steps of (a) preparing a green compact by compressing a raw material powder blend consisting of a Mo powder having an average particle size of not more than 20 mum and a transition metal powder having an average particle size of not more than 500 mum; (b) pulverizing the green compact to produce a secondary powder having an average particle size of from not less than an average particle size of the raw material powder blend to not more than 10 mm; (c) filling the secondary powder into a container for pressurizing; and (d) subjecting the secondary powder with the container for pressurizing to sintering under pressure thereby obtaining a sintered body of the target material.

Description

The method for preparing Mo alloy system target material
Technical field
The present invention relates to a kind of method for preparing Mo alloy system target material by powder sintering method.
Background technology
Now, will have low-resistance refractory metal for example the film of Mo be used for membrane electrode, film distribution of LCD (hereinafter referred to as LCD) etc., its metallic film generally is to be formed by the system target material that is used for sputter.In recent years, tend to larger sized LCD, need larger sized system target material thereupon, particularly, length is not less than the long size article of 1m, or the sputter area is greater than 1m 2The large scale article.
Traditionally, be adapted to the trend of larger sized sputter area, advised certain methods, comprise a large amount of original system target material section bars and the bonding method of backboard.But, method according to the bonding big content of starting materials system target material section bar of this use, this has proposed to splash owing to material is abnormal, the problem that comprises particle in deposit film, this is in sputter procedure because the gap that exists between the bonding raw material system target material part of vicinity separately produces.In order to overcome this problem, need to use integrated raw material system target material element.
Up to now, though for prepare refractory metal for example Mo the system target material and use powder sintering method, when preparation is this when having larger sized integrated raw material system target material, importantly how to obtain high density and larger sized material.Various powder sintering methods are arranged, and it comprises hip moulding method (hereinafter referred to as HIP).According to the HIP method, can apply high pressing pressure to material powder three-dimensionally, therefore advantageously, and to compare according to the hot pressing method that can be only applies high pressing pressure to the material powder plane, it can have high and density uniformly.
In the HIP method, before the pressurization material powder, the pressurization that needs effectively and equably the material powder of sintering to be packed into is with in the container.Therefore, advised that how some increase the method for pressure to the material powder of filling, for example these methods can referring to, JP-A-2002-167669 and JP-A-2003-342720.
But, even by the disclosed method for preparing Mo or Mo alloy system target material of top patent publications, when preparation comprises the system target material of one or more Mo alloys that add element, produced such problem, promptly occur one or more easily and add elements segregation, this problem can not solve by top method.In addition, also produced the problem of the unfavorable alteration of form of a pressurization and sintered body.
Summary of the invention
Summary of the invention
An object of the present invention is to provide a kind of method of system target material of the Mo of preparation alloy, according to this method, improved the density that the material powder in the container is used in the pressurization of packing into, reduced the problem of the disadvantageous alteration of form of pressurization and sintered body, and reduced the segregation of material component.
The inventor has studied the method for the system target material of various preparation Mo alloys, and discovery is packed into to pressurize by control and used the particle size of the raw material powder mixture in the container, can solve the above problems, and has therefore finished the present invention.
According to an aspect of the present invention, a kind of method of the Mo of preparation alloy system target material is provided, this method comprises following step: (a) be no more than the raw material powder mixture that the Mo powder of 20 μ m and transition metal powders that average particle size particle size is no more than 500 μ m are formed by compacting by average particle size particle size, prepare green compact; (b) pulverize green compact with the preparation secondary, its average particle size particle size is to be not less than the average particle size particle size of raw material powder mixture to being no more than 10mm; (c) secondary is encased in pressurization with in the container; (d) secondary and pressurization are carried out sintering with container under pressure, therefore obtain making the sintered body of target material.
According to an embodiment of top method, transition metal is to be selected from any among Ti, Zr, Hf, V, Nb, Ta, Cr and the W.
According to another embodiment of top method, after process (d), the sintered body that is sealed in the container is carried out thermoplasticity processing.
According to another embodiment of top method, after step (d), the sintered body that is sealed in the container is carried out thermoplasticity processing, heat treatment then is recrystallized.
Preferably, suppress raw material powder mixture by cold isostatic compaction.More preferably suppress being not less than under the pressure of 100MPa.
The relative density that preferred green compact have is not less than 50%.
Preferably, carry out the sintering under the pressure by the HIP method.The optimum condition of HIP method is 1000 to 1500 ℃ temperature and the pressure that is not less than 100MPa.The relative density of preferred sintered body is not less than 98%.
The container that secondary preferably is housed has the interior space that maximum length is not less than 1000mm.
The container that secondary preferably is housed is the can of cuboid form basically, and one face is as the import of the secondary of packing into, and this face is not less than 1000mm with respect to vessel bottom wall that forms depth capacity and space has in it maximum length.
Preferred thermoplastic processing be minification be 2 to 50% and temperature be repeatedly plastic working under 500 to 1500 ℃ the condition.
Heat treatment preferably is recrystallized under 1000 to 1500 ℃ temperature.
Preferably with the sintered body section, to obtain the sheet target material, so that keep the maximal side of sintered body.
According to the present invention, can reach above-mentioned purpose, promptly improved at the packing density of pressurization with the raw material powder mixture in the container, reduce the problem of the disadvantageous alteration of form of pressurization and sintered body, and reduced the segregation of material component.
Description of drawings
Figure 1 shows that vertical schematic side view of sintered body among the embodiment 1;
Fig. 2 is the photo in the Nb district that emanates in the metal structure that is used for being evaluated in No. 2 sample system target material of the present invention of embodiment 1;
Fig. 3 is the photo in the Nb district that emanates in the metal structure that is used for being evaluated in No. 9 sample system target material of the present invention of embodiment 1;
Fig. 4 is the photo of the microstructure of the 2-1-1 sample in embodiment 3, and it is to be that 100 light microscope is taken by amplifying figure place; With
Fig. 5 is the photo of the microstructure of the 2-1-3 sample in embodiment 3, and it is to be that 100 light microscope is taken by amplifying figure place.
Detailed Description Of The Invention
A main aspect of the present invention is that the method by following obtains the method for green compact: the raw material powder mixture that compacting is made up of Mo powder and transition metal powders, then green compact are pulverized, with the preparation secondary, its average particle size particle size is to be not less than the average particle size particle size of raw material powder mixture to being no more than 10mm, secondary pack into pressurization with in the container, therefore improve the packing ratio of secondary in the container, and reduced the segregation of material component.
By utilizing pressurization to prepare under the situation of Mo alloy system target material, use the Mo fine powder usually with the container sintered powder.But when packing the Mo powder in container, the distribution of the powdery components in container changes easily, because the Mo powder has high caking tendency and mobile poor.
In this, the inventor fully studies the back and finds, by regulating the particle size of raw material powder mixture, can improve the packing ratio of raw material powder mixture in the container, so that to a certain degree be big.On the other hand, under the situation of mixed Mo powder and other transition metal powders, the segregation of material component takes place easily, the caking tendency of this and powder, and the flowabilities of powder etc. are relevant.Therefore, the inventor also finds can address this problem effectively by following method: by suppressing the raw material powder mixture of being made up of Mo powder and transition metal, obtain green compact, then green compact are pulverized with the preparation secondary, and pack secondary into pressurization with in the container, improve pressurization thus with the segregation of the raw material powder mixture in the container and pressurization other segregation with the material component of sintered body in the container.
Below, will provide the detailed content of the inventive method.
Common Mo powder has thin particle size, and its average particle size particle size is no more than 20 μ m, because it is by chemical preparation.On the other hand, transition metal such as Nb, Cr, Ti have big relatively particle size, and its average particle size particle size is no more than 500 μ m, and ingot casting prepares because this powder is normally by pulverizing.In the present invention, green compact are preparations like this: by suppressing thin raw material powder mixture, then green compact are pulverized, to obtain secondary, its average particle size particle size is to be not less than the average particle size particle size of raw material powder mixture to being no more than 10mm.Secondary pack into pressurization with in the container, follow sintering under pressure, obtain being used to make the sintered body of target material raw material thus.
The reason that the lower limit of the average particle size particle size of secondary should be not less than the average particle size particle size of raw material powder mixture is: preparation and pulverize green compact to be lower than the secondary of raw material powder mixture average particle size particle size nonsensical to obtain average particle size particle size.The reason that the upper limit of the average particle size particle size of secondary should be no more than 10mm is: by tangible grain boundary occurring in the metal structure of average particle size particle size above the sintered body of the secondary preparation of 10mm, its metal structure has a kind of patterned appearance.This sintered body means the danger of local hyperoxia amount, because grain boundary preferentially contacts with air.Therefore, do not observe grain boundary in appearance, and for the particle size that makes secondary is even as far as possible, average particle size particle size should be no more than 10mm in order to make.
In the present invention, when mixed Mo and transition metal powders,, importantly prepare green compact and pulverize it, so that the average particle size particle size that obtains is no more than 10mm in order to suppress the segregation of mixed powder of transition metal and Mo powder.
Here, the qualification that provides is: in the particle size distribution of Mo powder, transition metal powders, raw material powder mixture or secondary, and 50% particle size (D of its total number of particles amount 50) be called average grain (or particle) size.
Preferably, the average particle size particle size of Mo powder of compacting is no more than 10mm, is no more than 5mm by pulverizing the average particle size particle size that secondary that green compact obtain has.
Reason is: particle size is more little, can easily obtain the high more relative density of sintered body.Consider that with the packing density of metal dust the container it is effective using the secondary of larger particle size from improving pressurization.But, consider that from sintering character preferred highdensity material powder has littler particle size.Particularly, consider that the Main Ingredients and Appearance of the sintered body by the inventive method preparation is Mo, because it is refractory metal and has high diffusion temperature usually, the preferred raw material powder mixture in the process vessel at high temperature improves the contact area of feed particles simultaneously.Therefore, the average particle size particle size of preferred Mo powder is no more than 10 μ m.The reason that the average particle size particle size of preferred secondary particle is no more than 5mm is: by this particle size, can reduce the local concentration of oxygen amount, and improve the decentralization of one or more interpolation elements in the Mo alloy.More preferably, the average particle size particle size of secondary is no more than 0.5 to 3mm.
In addition, the reason that is no more than 500 μ m with the average particle size particle size of the mixed transition metal powders of Mo powder is: if average particle size particle size surpasses this value, can not reduce the segregation of making component in the target material.
As for green compact,, preferably suppress it, so that the relative density that has is not less than 50% in order to keep being encased in the particle size of pressurization with the secondary in the container.
Be the raw material of Mo preferably, wherein preferably apply the pressure that is not less than 100MPa,, it is had be not less than 50% relative density with the raising green compact to material powder by cold isostatic pressing method (hereinafter referred to as CIP) compacting Main Ingredients and Appearance.
Preferably carry out raw material sintering under pressure by the HIP method because can be during sintering to material three-dimensional apply high pressure.The ideal conditions of HIP method is 1000 to 1500 ℃ temperature and the pressure that is no more than 100MPa.If the HIP method is at the pressure that is lower than 100MPa and is lower than under 1000 ℃ the temperature and carries out, side is difficult to prepare the needed relative density of target material and is not less than 98% sintered body.On the other hand, though in order to obtain the sintered body that key component is Mo, preferably carry out sintering under high as far as possible temperature, the processing temperature of HIP method is subjected to pressurizeing with the material category of container and the restriction of equipment.In common HIP device, the upper limit of processing temperature is about 1500 ℃.The temperature that is higher than 1500 ℃ is unpractical.
As for the size of pressurization with container, though there is a problem, promptly when using larger sized container, almost do not improve packing density and the component segregation takes place easily, the inventive method is applicable to preparation large scale system target material, and described large scale system target material requires to use maximum length to be not less than the pressurization container of 1000mm.Method as for container that powder is packed into, in order to utilize powder proportion to improve packing density, more preferably use the pressurization container, it is a cuboid form basically, one face is as the import of the secondary of packing into, this face is with respect to the vessel bottom wall that forms depth capacity, and the maximum length that space has in it is not less than 1000mm.Powder is packed into behind the container, it is desirable to make the powder in the top cover squeeze receptacle simultaneously by the top seal container.This is because by this top cover compaction of powders, can eliminate the redundant space of the top area of powder in the container, and the proportion of powder does not play a role to this zone, therefore reaches powder all even intensive occupied state from the top to the bottom in container.
According to a feature of the inventive method, the sintered body that is sealed in the container is carried out thermoplasticity processing, because being applicable to, this processing make sintered body have bigger size.
Sintered body is that with the reason that container carries out thermoplasticity processing if sintered body is processed under exposing to the open air on its surface, there is the danger of pollution on the surface of sintered body.Consider from another angle,, can save a process from sintered body, removing container, therefore can reduce production costs according to the processing method of this sintered body and container.
It is desirable to, thermoplasticity processing is repeatedly to carry out with 2 to 50% minification at every turn, keeps in 500 to 1500 ℃ of the temperature of sintering simultaneously.
If temperature is lower than 500 ℃, must improve the processing load that sintered body is applied, reason is the calenderability that it is low, therefore produces the problem of productivity ratio.On the other hand, if temperature surpasses 1500 ℃, there is the problem of the crystal grain roughening of the danger of container fusing and sintered body.If the minification of thermoplasticity processing surpasses 50%, be created in the problem that occurs in the sintered body breaking with internal flaw.If the minification of thermoplasticity processing is lower than 2%, sintered body is out of shape hardly, therefore produces the problem of waste production cost.In addition, the height that needs of sintered body dwindles under the situation of processing on the whole, and for fear of breaking or the generation of internal flaw, under the condition of described in the above temperature and minification, it is effective repeatedly processing.
According to another feature of the present invention, after thermoplasticity processing, to the sintered body heat treatment that is recrystallized.Rolling workpiece has the fibre metal structure, and the structure of this degree is in each section difference of workpiece, particularly at the surface portion of this workpiece and the core of thickness direction.Preferred system target material should have uniform crystal structure, because system target material crystal structure heterogeneous influences the uniformity of the deposit film that forms by sputter unfriendly.Therefore, preferably rolling workpiece is utilized the processing that homogenizes of recrystallization phenomenon, so that its crystal structure is even.
The heat treatment of preferred recrystallization is to carry out under 1000 to 1500 ℃ temperature.If temperature is not higher than 1000 ℃, very likely after heat treatment, keep the fibre metal structure, reason is that key component is the performance of the chemical composition of Mo.If temperature surpasses 1500 ℃, carry out height before appearing at and dwindle the part roughening of processing the surf zone generation crystal grain that runs into.
According to another feature of the present invention, to sintered body, comprise sintering only those, carry out thermoplasticity processing those and carry out thermoplasticity processing and recrystallization heat treatment those, cut into slices, obtain a plurality of sheet target materials, so that keep the maximum length of corresponding sintered body.The favourable part of this method is: according to the needs of large scale system target material, only by once pressurizeing and sintering process, prepare many system target materials.
It is desirable to, material powder material in the methods of the invention comprises and is not less than 50 atom %Mo.Consider that the Mo powder with high caking performance is difficult to pack into equably pressurization with in the container, in order to obtain comprising the system target material that is not less than 50 atom %Mo, it is very effective using material powder material of the present invention.
Below, will provide some embodiment to describe about the inventive method.
The specific embodiment
Embodiment 1
Nb powder, the average particle size particle size that the preparation average particle size particle size is the Mo powder of 12 μ m, W (tungsten) powder that average particle size particle size is 12 μ m, average particle size particle size is 100 μ m is that Ti powder and the average particle size particle size of 100 μ m is the Zr powder of 100 μ m.
Prepare the system target material of the 1st shown in the table 1 to No. 6 samples by following method, it is the present invention.
(1) in order to prepare every kind of sample, Mo powder and any transition metal powders of the specified rate represented with atom % of weighing.
(2) utilize the mixed powder of being weighed of V-type mixer 10 minutes, obtain material powder.
(3) by the CIP machine, under 265MPa pressure, suppress material powder, form green compact.
(4) utilize jaw crusher and disc mill to pulverize green compact, the preparation secondary.
(5) mix secondary 10 minutes at V-type mixer, then packing into pressurization is with in the container, and pressurization is made by low carbon mild steel with container, and the size in interior space is: thickness is that 100mm, width are 1000mm and highly are 1300mm.After the secondary of packing into, will have top cover and container welding, to seal its inlet except that gas port.
(6) under 450 ℃, vacuum, the container that secondary is housed is carried out degassing processing, then sealing removes gas port.After this, by the HIP machine, under pressure, with secondary with the container sintering.The operating condition of HIP machine is 1250 ℃ temperature, the pressure of 150MPa and 5 hours operating time.
The sintered body section that (7) will therefore obtain, and machining, preparing six sheet system target materials, its each have rectangular shape, its size is: thickness is that 6mm, width are that 810mm and length are 950mm.
(8) packing density of the secondary of measurement in container, its value is shown in Table 1.
(9) by Archimedes's method, take out sample from green compact and sintered body, check relative density respectively, its value is shown in Table 1.
In addition, in order to prepare the 7th and No. 8 reference sample system target material shown in the table 1, the preparation average particle size particle size is that Mo powder and the average particle size particle size of 6 μ m is the Nb powder of 100 μ m, and by above-mentioned same quadrat method processing, obtains sintered body.With section of every kind of sintered sheets and the machining that obtains thus, preparing six sheet system target materials, its each have rectangular shape, its size is: thickness is that 6mm, width are that 810mm and length are 950mm.
The packing density of the secondary in the measuring vessel, its value is shown in Table 1.
By Archimedes's method, from green compact and sintered body, take out sample, check relative density respectively, its value is shown in Table 1.
In order to prepare the 9th and No. 10 comparative sample system target material shown in the table 1, preparation Mo powder and Nb powder.Prepare the 9th and No. 10 comparative sample system target material shown in the table 1 by following method.
(1), weighs respectively and represent the Mo powder and the Nb powder of specified rate with atom % in order to prepare comparative sample the 9th and No. 10.
(2) utilize the mixed powder of being weighed of V-type mixer 10 minutes, obtain the material powder of the 9th and No. 10 comparative sample.
(3) every kind of pressurization of packing into of material powder of the 9th and No. 10 comparative sample is used in the container, do not carried out compression process, pressurization is made by mild steel with container.
(4) behind the charging feedstock powder, will have top cover and container welding, to seal its import except that gas port.
(5) under 450 ℃, vacuum, the container that secondary is housed is carried out degassing processing and sealing removes gas port.After this, by the HIP machine, under pressure, with secondary with the container sintering.The operating condition of HIP machine is 1250 ℃ temperature, the pressure of 150MPa and 5 hours operating time.
Every kind of sintered body section that (6) will therefore obtain and machining, preparing three sheet system target materials, its each have rectangular shape, its size is: thickness is that 6mm, width are that 610mm and length are 710mm.
(7) packing density of the secondary of measurement in container, its value is shown in Table 1.
(8) by Archimedes's method, take out sample from green compact and sintered body, check relative density respectively, its value is shown in Table 1.
As for all the 1st to No. 10 sample system target materials, assess the shape variation of sintered body separately, this variation occurs in during the sintering.It is the method for how assessing in order to describe that Fig. 1 is provided.This figure represents vertical schematic side view of sintered body model wherein to have reference point 3, the longitudinal center 2 of its bottom surface in sintered body model 1 (on the y axle) with the x-y coordinate.The left end of sintered body model 1 is bent upwards in the drawings, so that the minimum point 4 in sintered body model 1 left side departs from the x axle, it is a distance 5, distance 5 display shape degrees of variation.The assessment result of the shape degree of variation of sample is shown in Table 1 separately, and wherein letter b is meant that the shape degree of variation is not less than 12mm, and this has problem, and alphabetical A is meant that the shape degree of variation is lower than 12mm, assesses it for good.
Table 1
Sample number Chemical composition (atom %) The average particle size particle size of starting powder The average particle size particle size of secondary (mm) The pressurization size (mm) of container
Mo (μm) Add element (μ m)
1 Mo 12 - 1.4 100×1000×1300
2 95.0Mo-5.0Nb 12 100 1.1 100×1000×1300
3 95.5Mo-4.5Nb 12 100 1.2 100×1000×1300
4 70.0Mo-30.0Ti 12 100 1.3 100×1000×1300
5 65.0Mo-35.0W 12 12 1.2 100×1000×1300
6 91.6Mo-8.4Zr 12 100 1.5 100×1000×1300
7 Mo 6 - 0.8 100×1000×1300
8 95.0Mo-5.0Nb 6 100 0.8 100×1000×1300
9 95.0Mo-5.0Nb 12 100 - 100×1000×1300
10 Mo 12 - - 100×1000×1300
The relative density of green compact (%) The packing density (%) of pressurization in the container The size of sintered body (mm) The relative density of sintered body (%) The assessment of shape degree of variation Remarks
69.0 53.0 81×816×1054 98.2 A Reference sample
71.0 54.0 81×817×1053 98.3 A The invention sample
70.0 53.5 81×815×1052 98.4 A The invention sample
69.5 53.0 80×813×1054 98.3 A The invention sample
70.0 53.5 81×816×1054 98.1 A The invention sample
69.0 52.5 81×812×1049 98.2 A The invention sample
68.0 58.5 83×835×1088 99.6 A Reference sample
69.0 60.0 84×844×1097 99.4 A The invention sample
- 39.5 73×735×955 98.3 B Comparative sample
- 38.5 72×729×945 98.1 B Reference sample
As shown in table 1, in the 1st to No. 8 the present invention and reference sample, because average particle size particle size is no more than the secondary of 10mm, respectively by pulverizing the green compact preparation, described green compact are by the preparation of compacting material powder, the packing density of the secondary in the 1st to No. 8 sample is not less than 52%, and this is very high.Thus, find out to have satisfied output ground preparation system target material, because because high packing density has reduced the space contraction and the shape variation of sintered body.
Referring to No. 8 samples of the present invention in the table 1, find out the secondary that the raw material powder mixture that utilizes average particle size particle size to be no more than 10 μ m and average particle size particle size are no more than 1mm, greatly improved packing density and relative density.
On the other hand, as for No. 9 comparative sample, wherein under the condition that does not have compacting, raw material powder mixture directly pack into pressurization with in the container, and carry out sintering under pressure, when preparation system target material, yield poorly, reason is to be no more than 40% low sizing density, and because shrink in the space of sintered body and the shape variation is big.In addition, even the container of use and the same size of other situation has because the space of sintered body is shunk big and shape makes a variation greatly, can not prepare to have the danger that needs the system of size target material.
Fig. 2 and 3 expressions are respectively applied for the photo of the Nb zone segregation of the metal structure in No. 2 sample of the present invention of assessment and No. 9 comparative sample.Under the situation of No. 9 comparative sample that does not wherein prepare secondary shown in Figure 3, exist major axis to be not less than the Nb zone of 20mm at the photo center.Thus, find out that the Nb segregation produces.On the other hand, under the situation of No. 2 sample of the present invention shown in Figure 2, the Nb zone is dispersed in the Mo matrix, does not therefore have tangible Nb segregation.
Embodiment 2
Have that to be shown in the sintered body with those identical chemical compositions No. 2 sample of the present invention and same size among the embodiment 1 be to prepare by the mode identical with the situation of No. 2 sample of the present invention, after the HIP process, in temperature is that 1150 ℃ and minification are no more than under 50% the condition, and it is carried out hot rolling three times with pressurization with container.The ideal dimensions of system target material is: width is that 1500mm and length are 1800mm.The rolling of sintered body the results are shown in the table 2.
Table 2
Sample number Chemical composition (atom %) The size of sintered body (mm) Target size in rolling (mm) Heating-up temperature (℃)
2-1 95.0Mo-5.0Nb 81×812×1053 25.7×1500×1800 1150
Table 2 (continuing)
Total rolling minification (%) Rolling minification (%) for the first time Rolling minification (%) for the second time Rolling for the third time minification (%) The result
68 20 30 43.5 Do not have cracked
As seen from Table 2, by being that 500 to 1500 ℃ and minification are to be rolled under 2 to 50% the condition in heating-up temperature, can preparing large-sized system target raw material and do not occur breaking.
Should be noted that when to sintered body when being rolled for 450 ℃ because low heating-up temperature can not keep the ductility of sintered body, cause unfriendly carrying out rolling must the circulation of the minification of several percentages.
Embodiment 3
To the heat treatment that in 900 ℃, 1150 ℃ and 1300 ℃, vacuum, is recrystallized respectively of the system target material of hot rolling among the embodiment 2.After will making target material and being heated to heat treatment temperature, kept temperature 1 hour, after this cool off workpiece.From three types workpiece, take out 2-1-1,2-1-2 and 2-1-3 sample respectively.Utilizing multiplication factor is the microstructure of 100 the mutual comparative sample of light microscope.That observes the results are shown in the table 3.As for the heat treated sample that is recrystallized under the temperature of 900 ℃ and 1300 ℃ respectively, providing respectively in Figure 4 and 5 and utilizing multiplication factor is the photo of the sample microstructure that shows of 100 light microscope.
Table 3
Sample number Chemical composition (atom %) The recrystallization heat treatment temperature (℃) Microstructure
2-1-1 95.0Mo-5.0Nb 900 Keep the fibre metal structure
2-1-2 95.0Mo-5.0Nb 1150 Isotropic structure
2-1-3 95.0Mo-5.0Nb 130 Isotropic structure
From table 3, Figure 4 and 5 as can be seen, when the recrystallization heat treatment temperature is lower than 1000 ℃, there is the possibility that keeps fibre structure.

Claims (11)

1. method for preparing Mo alloy system target material, this method comprises following step:
(a) be no more than the raw material powder mixture that the Mo powder of 20 μ m and transition metal powders that average particle size particle size is no more than 500 μ m are formed by compacting by average particle size particle size, prepare green compact;
(b) pulverize green compact with the preparation secondary, its average particle size particle size is to be not less than the average particle size particle size of raw material powder mixture to being no more than 10mm;
(c) secondary is encased in pressurization with in the container; With
(d) secondary and pressurization are carried out sintering with container under pressure, therefore obtain making the sintered body of target material.
2. according to the process of claim 1 wherein that transition metal is to be selected from any among Ti, Zr, Hf, V, Nb, Ta, Cr and the W.
3. according to the process of claim 1 wherein after sintering process (d), the sintered body that is sealed in the container is carried out thermoplasticity processing.
4. according to the method for claim 3, wherein thermoplasticity processing be minification be 2 to 50% and heating-up temperature be repeatedly plastic working under 500 to 1500 ℃ the condition.
5. according to the process of claim 1 wherein after step (d), the sintered body that is sealed in the container is carried out thermoplasticity processing, heat treatment then is recrystallized.
6. according to the method for claim 5, wherein thermoplasticity processing be minification be 2 to 50% and heating-up temperature be repeatedly plastic working under 500 to 1500 ℃ the condition.
7. according to the method for claim 6, the heat treatment that wherein is recrystallized is to carry out under 1000 to 1500 ℃ temperature.
8. according to the process of claim 1 wherein that the pressing process in step (a) is to be undertaken by the cold isostatic compaction under the pressure that is being not less than 100MPa.
9. according to the process of claim 1 wherein that sintering process in sintering process (d) is by carrying out at 1000 to 1500 ℃, the hip moulding that is not less than under the pressure of 100MPa.
10. according to the method for claim 1, the container that secondary wherein is housed is the can of cuboid form basically, one face is as the import of the secondary of packing into, and this face is not less than 1000mm with respect to the vessel bottom wall of formation depth capacity and the maximum length that space has in it.
11.,, obtain many sheet target materials so that keep the maximal side of sintered body wherein with the sintered body section according to the method for claim 10.
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