CN103459631A - Molybdenum material - Google Patents
Molybdenum material Download PDFInfo
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- CN103459631A CN103459631A CN2012800143292A CN201280014329A CN103459631A CN 103459631 A CN103459631 A CN 103459631A CN 2012800143292 A CN2012800143292 A CN 2012800143292A CN 201280014329 A CN201280014329 A CN 201280014329A CN 103459631 A CN103459631 A CN 103459631A
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- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
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- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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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
- B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
- B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
- B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
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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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract
The present invention addresses the problem of providing an industrially advantageous molybdenum material which is capable of secondary recrystallization at a temperature lower than that of a conventional molybdenum material and which can be converted through the secondary recrystallization into a material that has a structure comprising very large grains with reduced grain boundaries and thus exhibits excellent creep resistance. When analyzed by X-ray diffraction measurement, this molybdenum exhibits, in the whole or part of the region corresponding to a sheet-thicknesswise depth of one fifth of the whole thickness from the surface, areas which each contain such a domain that the peak intensities of the (110) and (220) diffraction planes are each lower than the peak intensity of the (211) diffraction plane.
Description
Technical field
The present invention relates to a kind of Mo.
Background technology
Mo sometimes is used to the requirements such as high-temperature structural material and component materials and at high temperature has stable on heating position.But, for the pure Mo of in material, not having a mind to add element-specific, if, approximately using more than 1000 ℃, recrystallize, be changed to the equi-axed crystal tissue.Produce when equi-axed crystal is organized and easily cause Grain Boundary Sliding, thereby cause anti-creep properties to descend, consequently easily deform.
Therefore, in the situation that the applied at elevated temperature Mo more than 1000 ℃ need to improve the anti-creep properties under high temperature.
As the method for improving the anti-creep properties of Mo under hot conditions, have even known more than recrystallization temperature is increased to use temperature or form recrystallize to occur and the anti-creep properties any means of excellent tissue still.
Wherein, as described in non-patent literature 1, as the method that improves recrystallization temperature, known have by using TZM alloy (molybdenum alloy that contains titanium, zirconium, carbon) to improve the method (non-patent literature 1) of primary recrystallization temperature.But the recrystallization temperature of TZM alloy is 1400 ℃ of left and right, though to compare this recrystallization temperature higher with pure Mo, after recrystallize, can form equi-axed crystal tissue, so under the condition more than recrystallization temperature with the same easy the deforming of pure Mo.
In addition, the anti-creep properties method of excellent material still as even recrystallize form to occur, known have a following method: as described in non-patent literature 2 by combination Al, Si, K, form thus the tissue that makes after the recrystallize lamination tissue along the crystal grain of growing up of machine direction elongation; Or as described in non-patent literature 3 by having added La
2o
3implement the plastic working of high working modulus Deng the molybdenum sintered compact of rare-earth oxide, form thus the tissue make after the recrystallize lamination tissue (non-patent literature 2,3) along the crystal grain of growing up of machine direction elongation.But, Mo is being forged or during plastic working that rolling is such, become for additive or the organizational controls that improves characteristic the reason that causes producing be full of cracks, have influence on the decline of the yield rate of salable product, also can produce in addition the anisotropy due to the curved characteristic of organizing anisotropy to cause etc., therefore need restriction Mo size.Further, in the situation that for as fire with backing plate, Mo and the purposes that thing etc. contacts of firing formed by other elements, sometimes the thing etc. fired contacted with Mo reacts with the additive in Mo, and likely the kind of thing is fired in restriction.
On the other hand, improve the method for anti-creep properties as the pure Mo good to plastic working, have the method for the crystal grain gigantism that has utilized secondary recrystallization to cause.This be due to: if make the crystal grain gigantism, the crystal crystal boundary reduces, thereby is difficult to cause the slippage of crystal boundary, as significant example, can enumerate monocrystal material.
Secondary recrystallization is described herein, be for example in the situation of Mo, by carrying out the thermal treatment of 1000 ℃～1100 ℃, it is core that the fibrous tissue formed by plastic workings such as rollings be take the strain produced by plastic working, again be changed to the crystal grain of 20 μ m～30 μ m left and right, this phenomenon is called to primary recrystallization or only is called recrystallize, further at high temperature, the material consisted of this primary recrystallization crystal grain is heat-treated, adjacent primary recrystallization crystal grain combination repeatedly thus, grow up, be changed to huge crystal grain, this phenomenon is called to secondary recrystallization (non-patent literature 4).
More specifically, the crystal grain of tens of microns left and right after primary recrystallization along with heat supply slowly gigantism to tens of microns～hundreds of microns, but for example when reaching certain temperature, or when certain temperature has been carried out long-time heating, can sharply grow up, form the above crystal grain of millimeter unit.Such crystal grain sharply gigantism phenomenon is called secondary recrystallization.
Therefore, in patent documentation 1, be that the crystal grain control processing that the molybdenum board material more than 99.9% carries out 0.5 hour～5 hours in the hydrogen stream of 2250 ℃ forms the huge discoideus crystal grain that diameter is 15mm～150mm to the purity of not adding in fact additive, can be formed in thus the sheet material (patent documentation 1) of 1800 ℃ of anti-creep properties excellences.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 61-143548 communique
Non-patent literature
Non-patent literature 1:T.Mrotzek et.al., " Hardening mechanisms and recrystallization behaviour of several molybdenum alloys " International Journal of Refractory Metals& Hard Materials, 2006, (24), p298-305.
Non-patent literature 2:Y.Fukasawa et.al., " Very High Temperature Creep Behavior Of P/M Molybdenum Alloys ", Proceedings of the11th International Plansee Seminar, vol.11985, p295-308.
Non-patent literature 3:R.Bianco et.al., " Mechanical Properties of Oxide Dispersion Strengthened (ODS) Molybdenum ", Molybdenum and Molybdenum Alloys Edited by A.Crowson, E.S.Chen, J.A.Shields, and P.R.Subramanian, 1998, p125-142.
Non-patent literature 4:(society) the powder Powder Metallurgy Organized is compiled " powder powder metallurgy term dictionary ", Nikkan Kogyo Shimbun ((society) powder Fen end Ye Jin Association meeting Knitting " powder powder metallurgy Language dictionary ", the new Wen of daily magazine industry society), 2001, p558～559.
Summary of the invention
The problem that invention will solve
Therefore the described technology of patent documentation 1 is not used additive, can be described as a kind of good technology, and the be full of cracks while there is no above-mentioned plastic working produces, without the problem of salable product decrease in yield; And do not have and fired the problem that thing reacts; And also do not need the plastic working of high working modulus, thereby the anisotropic of amorphous anisotropy and characteristic.
But, for the described molybdenum board material of patent documentation 1, the thermal treatment temp needed in order to produce secondary recrystallization is 2250 ℃, if starting temperature from primary recrystallization is that 1000 ℃ are considered, said temperature is very high, from productivity and these aspects of cost of energy, expectation further reduces the needed thermal treatment temp of generation secondary recrystallization.
The present invention completes in view of the above problems, its purpose is to provide a kind of Mo, this Mo has the industrialness advantage, compared with the past, can cause secondary recrystallization with low temperature, and can make the tissue huge crystal grain few by crystal boundary after secondary recrystallization form and anti-creep properties excellence.
In order to address the above problem, the inventor is conceived to the intensity of each crystalline diffraction face based on X-ray diffraction of Mo and the relation of secondary recrystallization behavior, and conduct in-depth research, found that: for the thickness direction of Mo, between the peak intensity of the specific crystalline diffraction face of certain area and secondary recrystallization temperature, have important relationship.
Further found, by controlling described peak intensity, compared with conventional art, can cause with low temperature the gigantism of the crystal grain based on secondary recrystallization, thereby complete the present invention.
; the 1st mode of the present invention is a kind of Mo; it is characterized in that; corresponding to being that in the zone of 1/5th the degree of depth of total thickness, at least a portion has part as described below along thickness direction apart from surface: carry out in the situation of X-ray diffraction mensuration, this part has the zone that crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
The 2nd mode of the present invention is a kind of Mo, it is characterized in that, this Mo is in the temperature more than 1700 ℃, the described Mo of the 1st mode to be heat-treated and obtained, and the median size based on segment method of the crystal grain in described sheet material cross section is more than 15mm.
The 3rd mode of the present invention is a kind of process furnace structure unit, it is characterized in that, this process furnace has the described Mo of the 1st or the 2nd mode with structure unit.
The 4th mode of the present invention is that a kind of firing used backing plate, it is characterized in that, this is fired with backing plate has the described Mo of the 1st or the 2nd mode.
The effect of invention
Can provide a kind of Mo in the present invention, it has the industrialness advantage, compared with the past, can cause secondary recrystallization with low temperature, and can make the tissue huge crystal grain few by crystal boundary after secondary recrystallization form and anti-creep properties excellence.
The accompanying drawing explanation
Fig. 1 illustrates the face of molybdenum board material of the present invention and the stereographic map of rolling direction.
Fig. 2 is the part stereographic map of molybdenum board material of the present invention.
Fig. 3 is for the figure of line segment ratio juris is described.
Fig. 4 A is the mode chart of organizing shape and size that molybdenum board material of the present invention is shown, and means the figure that organizes shape and size after rolling.
Fig. 4 B is the mode chart of organizing shape and size that molybdenum board material of the present invention is shown, and means the figure that organizes shape and size after primary recrystallization.
Fig. 4 C is the mode chart of organizing shape and size that molybdenum board material of the present invention is shown, and means the figure that organizes shape and size after secondary recrystallization.
Fig. 5 is the figure that the X-ray diffraction result of the molybdenum board material that embodiments of the invention relate to is shown.
Fig. 6 is the figure that the X-ray diffraction result of the molybdenum board material that comparative example relates to is shown.
Fig. 7 means the table of the relation of the Heating temperature of embodiment and the related molybdenum board material of comparative example and crystal particle diameter.
Fig. 8 is the schematic diagram of the load test estimated for the anti-creep properties of embodiment and the related molybdenum board material of comparative example.
Fig. 9 means the table of result of the load test of the molybdenum board material that embodiment and comparative example relate to.
Embodiment
Below, with reference to accompanying drawing, the preferred embodiment of the present invention is elaborated.
As mentioned above, Mo of the present invention is that the peak intensity to the specific crystalline diffraction face of certain area on thickness direction has carried out the material of controlling, below, for the condition of Mo of the present invention, the sheet material of take is elaborated as example.
<form
For the composition of molybdenum board material of the present invention, main component is that molybdenum gets final product.
Particularly, as consider to for example on molybdenum board material of the present invention, carry out heat treated fire thing at high temperature use sheet material of the present invention the time material that is in contact with it pollution, preferably by the molybdenum more than 99.9 quality %, formed, but be not limited to this.The material that the molybdenum of for example take is main component (more than 98 quality %) more specifically, for example, contains the lanthanum-oxides (La of 0.1 quality %～2.0 quality % in molybdenum
2o
3) sheet material; Or the sheet material of carbon that contains zirconium, the 0.01 quality %～0.1 quality % of titanium, the 0.01 quality %～0.10 quality % of 0.3 quality %～1.0 quality % in molybdenum also can similarly obtain causing the secondary recrystallization texts with the temperature lower than in the past.That is, molybdenum board material and additive form alloy and also can obtain same effect.
<manufacture method >
Molybdenum board material of the present invention is that molybdenum powder is carried out to extrusion forming/sintering, and it is implemented to the plastic working such as rolling or forging and the material that obtains.Below, the method for processing to obtain molybdenum board material by rolling is described, but, so long as peak intensity based on X-ray diffraction of the present invention can be controlled, manufacture method is not limited to this.
The preferred purity of molybdenum powder of using in order to obtain molybdenum board material of the present invention is more than 99.9 quality %.For powder characteristics such as the particle diameter of raw material powder and volume densities with for the suppression process that obtains sintered compact and method and the condition of sintering circuit, as long as can access the density that can carry out the plastic working degree, be that relative density is the sintered compact more than 90% in addition.
It should be noted that, the relative density of sintered compact is less than in 90% situation, when sheet material is carried out to plastic working, because the space in sintered compact causes producing be full of cracks etc., is not therefore preferred.
Extrusion forming method as molybdenum powder, for example, use by Fsss method (Fischer's method, Ficsher Sub-Sieve Sizer) molybdenum powder that the granularity of measuring is 1.0 μ m～10 μ m, use well-known single axle press or isostatic cool pressing press (CIP) etc. to carry out extrusion forming, form thus formed body and get final product.In addition, as the sintering method of formed body, can be in the non-oxidizing atmospheres such as hydrogen, argon gas, vacuum above-mentioned formed body be carried out to the heat treated of 1700 ℃～2000 ℃ and carry out sintering.
In addition, except the molybdenum of main component, have in the situation of additive, for additive is dispersed in sintered compact, in addition also in order not make the yield rate variation in the plastic working after sintering, can suitably set the powder characteristics such as the purity of additive and granularity.
Rolling processing for sintered compact, by the roller interval of controlling every 1 passage, be Reduction by rolling (=((thickness before rolling)-(thickness after rolling)) * 100/ (thickness before the rolling) % of unit), control thus the intensity of particular crystal plane in the X-ray diffraction in following zone, described zone refers to the zone of 1/5th the degree of depth that is equivalent to thickness of slab along the thickness of slab direction apart from surface arbitrarily of at least 1 face in the opposite face up and down of sheet material.Product of the present invention can be controlled according to as described below: make the Reduction by rolling of every 1 passage of rolling be less than for 20% (not comprising 0), make thus while carrying out X-ray diffraction mensuration, in the zone of 1/5th the degree of depth that is equivalent to thickness of slab along the thickness of slab direction apart from surface arbitrarily of at least 1 face of the opposite face up and down of sheet material, crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
Make the working modulus of every 1 passage of rolling be less than 20% herein, because this is the condition that guarantees to control the intensity of specific crystalline diffraction face of the present invention, if Reduction by rolling is to be difficult to control the intensity of crystalline diffraction face more than 20%, also can breaks etc. and to cause reducing the salable product yield rate due to rolling in addition.In addition, under the Reduction by rolling of every 1 passage, be limited to more than 5%, more preferably more than 15%.This be due to: in the situation that be less than 5%, can increase the rolling pass number and cause manufacturing cost to increase.
In addition, the thickness for the sintered compact for obtaining molybdenum board material of the present invention is not particularly limited.Therefore, for example, for the sheet material that to obtain thickness be 20mm, the thickness of sintered compact is that 50mm or 150mm all can.
Herein, if rolling general working rate (=(thickness of sintered compact)-(final thickness of the sheet material after rolling) * 100/ (thickness of sintered compact) % of unit) is not to be at least more than 50%, be difficult to obtain X-ray diffraction peak intensity of the present invention.More preferably more than 85%.
In order to meet working modulus and the general working rate of above-mentioned every 1 time, need to carry out tens processing (rolling pass number), for example 20 times.Than implementing repeatedly processing (rolling pass number), the boundary of the rolling rate of every 1 time is set as to 20% and the surface of the molybdenum board material that obtains and inner X-ray diffraction line graph have a great difference with it.
The mode chart of the crystalline structure of resulting molybdenum board material is shown in to Fig. 4 A.Form fibrous tissue by rolling.
<X-ray diffraction intensity >
Then, the X-ray diffraction intensity of the crystal face of sheet material of the present invention is described.The schematic diagram of sheet material shown in Fig. 1.The ND face of sheet material is the face be rolled, the face contacted with Rolling roller, corresponding to the top and bottom of the defined sheet material of present embodiment.
For molybdenum board material of the present invention, carry out in the situation of X-ray diffraction mensuration, in the zone of 1/5th the degree of depth that is equivalent to thickness of slab along the thickness of slab direction apart from surface of at least 1 face of the opposite face up and down of sheet material, at least a portion has part as described below: this part has the zone that crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
; 1/5th the zone that is equivalent to thickness of slab along the thickness of slab direction apart from surface arbitrarily of at least 1 face of the opposite face up and down that the significant points (controlling the zone of the X-ray diffraction intensity of molybdenum board material) of as shown in Figure 2, in the present invention, secondary recrystallization being brought to the sheet material of remarkably influenced is sheet material.
It should be noted that, " 1/5th the zone that is equivalent to thickness of slab " is the scope that essence surface that span has been removed the sheet material after the oxide compound inevitably produced on the surface of plastic working material is equivalent to 1/5th the degree of depth ± 50 μ m herein.In addition, the removal oxide compound refers to by the heat reduction in hydrogen atmosphere and processes; Utilize the chemical treatments of the mixed solution etc. of chloroazotic acid or hydrofluoric acid and nitric acid; Machinery based on cutting or grinding is removed; Or their combination removes the oxide skin on the surface produced in processing, this process is implemented after the rolling process finishing.
In addition, opposite face up and down to the control of the intensity of crystalline diffraction face for sheet material carries out, at least 1 face for the ND face of Fig. 1 carries out, this be due to: as long as any one side of top and bottom is controlled, by the thermal treatment more than 1700 ℃, will make that molybdenum board material is whole produces secondary recrystallization, thereby the plate cross section, be that the median size of the crystal grain of TD face or RD face in Fig. 1 is more than 15mm.Limitting in addition the distance on distance plate surface is owing to having found that the X-ray diffraction intensity that is equivalent to the zone of thickness of slab 1/5th apart from the plate surface brings remarkably influenced to secondary recrystallization.
While making the peak intensity of crystalline diffraction face be above-mentioned condition, can it be unclear that in the concrete mechanism of the generation of the temperature lower than in the past secondary recrystallization, but the recrystallize phenomenon of crystal grain comprises primary recrystallization and secondary recrystallization, described primary recrystallization is the crystal grain of molybdenum board material to be implemented to the processing such as rolling or forging to form strain, it is carried out to heat treated and cause the strain opening and take the strain that produced by processing again forming as core.Secondary recrystallization is to produce described primary recrystallization crystal grain gigantism and fit phenomenon, it is believed that for the Mo the present invention relates to brings the reason of considerable influence to be to phenomenon of secondary recrystallization: the state of the Mo before primary recrystallization, the peak intensity that the position that forms the core of recrystallize is present in the crystalline diffraction face meets the zone of above-mentioned condition.
, sometimes only with 1 face of the ND face of Fig. 1, mean X-ray diffraction intensity of the present invention as mentioned above herein, this is because the plastic working condition determines, be rolled processing such as the sheet material to molybdenum in sheet material add the conditions such as reversion of the top and bottom in man-hour.On the other hand, top and bottom have been carried out in the situation of rolling equably, the two sides of ND face easily presents X-ray diffraction intensity of the present invention.
It should be noted that, all X-ray diffraction intensities that are equivalent to 1/5th zone that might not need whole of plate surface meet above-mentioned condition, as long as there is the part that meets above-mentioned condition at least a portion of plate surface, can take this part as basic point generation secondary recrystallization.
<primary recrystallization temperature >
The primary recrystallization temperature is the difference more or less due to the difference of processing conditions generally, but, probably 1000 ℃～1100 ℃ left and right, for sheet material of the present invention, with material was the same in the past, be 1000 ℃～1100 ℃ left and right.
The mode chart that the primary recrystallization tissue has been shown in Fig. 4 B is convenient for reference.For generation of the atmosphere of primary recrystallization so long as non-oxidizing atmosphere just be not particularly limited.Such as enumerating hydrogen, argon gas, vacuum atmosphere etc., can be also the atmosphere formed by aforesaid combination.
<secondary recrystallization temperature >
Then, in order to make molybdenum board material in the present invention, produce secondary recrystallization, need to heat-treat more than 1700 ℃.This be due to: for prior art, in the situation that be less than this temperature, for example when carrying out 10 hours heat treated for 1600 ℃, be difficult to produce secondary recrystallization.It should be noted that, need about 10 hours the heat-up time under 1700 ℃ of conditions, if but reach over above-mentioned temperature, in the shorter time, produce secondary recrystallization.Atmosphere while heat-treating in addition is the same with the situation of above-mentioned primary recrystallization.
<secondary recrystallization particle diameter >
More than when more than 1700 ℃, molybdenum board material of the present invention being heat-treated, the median size of the crystal grain in plate cross section is preferably 15mm.This be due to, it is to obtain the good needed crystal particle diameter of anti-creep properties.The spent economical load for the treatment of temp and treatment time of take in patent documentation 1 in addition is reason, and maximum crystal particle diameter is 150mm, if but use product of the present invention, can under than lower temperature/short period of time condition, make the crystal grain gigantism, also can form monocrystalline according to condition.In addition, even the size of sheet material increases, if prepare to heat-treat big or small process furnace to it, size that can corresponding sheet material makes the crystal particle diameter after secondary recrystallization become large, and therefore maximum crystal particle diameter is unrestricted.
It should be noted that the mean value that said average crystalline particle diameter is situation as described below herein: as shown in Figure 3, for 1 test film, draw 3 parallel lines arbitrarily in the sheet material top and bottom, calculate the crystal particle diameter on line separately.
It should be noted that, Mo of the present invention is substantially unrestricted to size.The size of Mo is that plastic working devices such as process furnace or rolling, forging, wire drawing etc. determine by manufacturing installation.As an example, can obtain Mo of the present invention in the inventor's test, it is the large-sized sheet material of long 1500mm, wide 1000mm, thick 20mm.
Embodiment
Below, based on embodiment, the present invention is further elaborated.
(embodiment 1 and comparative example 1)
Make molybdenum board material with various processing conditions, peak intensity and the relation of secondary recrystallization temperature and the anti-creep properties after secondary recrystallization etc. of thickness of slab direction are estimated.Concrete order is as described below.
The making of the test portion of<embodiment 1 >
Using purity is that 99.9 quality % and the granularity measured by the Fsss method molybdenum powder that is 4 μ m is as starting raw material.Be filled in rubber by this molybdenum powder and utilize CIP (cold isostatic press, Cold Isostatic Pressing) with 2ton/cm
2pressure be pressed, carry out 10 hours sintering with 1800 ℃ in hydrogen stream, thereby obtained 2 sintered compacies that wide 300mm, long 400mm and thickness are 20mm and 150mm.The relative density of the sintered compact obtained is respectively 94.2%, 94.4%.
This sintered compact, after 1500 ℃ of heating 20 minutes, is repeatedly carried out the rolling of 2～3 passages and, 1200 ℃ reheat, finally obtains the molybdenum board material that thickness of slab is 1.0mm, 1.5mm, 2.0mm, 3.0mm, 10mm, 20mm.In embodiments of the invention 1, the sintered compact that the sheet material of thickness of slab 1.0mm～3.0mm is 20mm to thickness is rolled to be made, and the sintered compact that the sheet material of thickness of slab 10mm, 20mm is 150mm to thickness is rolled to be made.
Herein, test portion for embodiment 1, the Reduction by rolling of every 1 passage (=((thickness before rolling)-(thickness after rolling)) * 100/ (thickness before the rolling) % of unit) is set as being less than 20%, is particularly 10%～19.8%.
Finally, in hydrogen atmosphere, with 800 ℃, reduce after processing and utilize chloroazotic acid to remove surperficial oxide compound, utilize afterwards pure water to be cleaned, thereby obtained the test portion of embodiment 1.
<X-ray diffraction >
Then, according to following order, the test portion obtained is carried out to X-ray diffraction analysis, measure the peak intensity of thickness of slab direction.
At first, use water-proof abrasive paper (No. #100～No. #1000) to carry out wet grinding to the ND face (rolling surface) of test portion, test portion after grinding is immersed in to electrolytic solution and (crosses chloric acid: ethanol=1:9), carry out the electrolytic polishing of 150 seconds with electric current 1A, test portion is ground to the thickness of slab direction degree of depth of carrying out X-ray diffraction.
Then, the X-ray diffraction device (RAD-2X) that utilizes the Rigaku of Co., Ltd. to manufacture, used Cu pipe ball, take tube current as 30mA, tube voltage be 40kV, sweep velocity: 1 degree (deg)/min; Divergent slit: 1 degree (deg); Scatter slit: 1 degree (deg); Light inlet slot: 0.15mm; Measure the conditions of angle 2 θ=30 degree～120 degree (deg) and carry out the X-ray diffraction of test portion, the size of the intensity of (110), (220) of exported measurement result, (211) face is compared.It should be noted that, resulting data are automatically the raw data of measuring is carried out background process, smoothing techniques and removed the result obtained after K α 2 by device software herein.
Then, again carry out above-mentioned grinding, test portion is ground to the thickness of slab direction degree of depth of carrying out X-ray diffraction, in this degree of depth, carry out X-ray diffraction.Until the regulation the degree of depth till the repeated multiple times aforesaid operations that carries out, to its at every turn the variation of the peak intensity of the thickness of slab direction of the ND face based on X-ray diffraction measured.
1 example (sheet metal thickness is 1.5mm) of variation of peak intensity of thickness of slab direction of the ND face based on X-ray diffraction of resulting molybdenum board material has been shown in table 1, shown in Fig. 5, table 1 has been carried out to the result of pictorialization.
[table 1]
Obviously known according to table 1 and Fig. 5: near the strength ratio of (211) thickness of slab direction central authorities is higher than (110), (220), and the intensity of (110), (220) is to approach 0 value.In the zone of surperficial 300 μ m (be equivalent to thickness of slab 1/5th), the intensity of (110), (220) is less than the intensity of (211) in addition.In other test portions of embodiment 1, the distribution of each crystal face also is same tendency.
It should be noted that, crystalline structure is the state of the mode chart representative of Fig. 4 A.
<composition measuring result >
Then, the composition of the test portion that obtains is measured.
Particularly, the luminescence of plasma analytical equipment ICPS-8100 that uses Shimadzu Seisakusho Ltd. to manufacture is measured metal ingredient.As gaseous impurities, O, C are measured, the TC-600 that uses respectively LECO company to manufacture is measured O, and the WC-230 that uses LECO company to manufacture is measured C.
Consequently: the composition of test portion consists of the molybdenum more than 98.0 quality % and other inevitable impurity.It should be noted that, as inevitable impurity herein, it is Al, Ca, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, Sn, Ti, Zr, Zn metallic impurity and O, C gaseous impurities, removes the purity of these materials as molybdenum purity.
The making of the test portion of<comparative example 1 and X-ray diffraction >
Obtaining similarly to Example 1 wide 300mm, long 400mm and thickness is 2 sintered compacies of 20mm and 150mm, to this sintered compact 1500 ℃ the heating 20 minutes after, repeatedly carry out the rolling of 2～3 passages and, 1200 ℃ reheat, finally obtain the molybdenum board material that thickness of slab is 1.0mm, 1.5mm, 2.0mm, 3.0mm, 10mm, 20mm.The Reduction by rolling of every 1 passage is set as to 20%～23% herein.It should be noted that, in the same manner as in Example 1, the sintered compact that the sheet material of thickness of slab 1.0mm～3.0mm is 20mm to thickness is rolled to be made, and the sintered compact that the sheet material that thickness of slab is 10mm, 20mm is 150mm to thickness is rolled to be made, thereby has obtained the test portion of comparative example 1.
Use the test portion that in above-mentioned comparative example 1, thickness of slab is 1.5mm, measure in the same manner as in Example 1 the variation of the X-ray diffraction intensity of thickness of slab direction, obtain the result as shown in table 2 and Fig. 6.
[table 2]
As shown in table 2 and Fig. 6, for the test portion of comparative example 1, in this sheet material, crystalline diffraction face (110) and (220) peak intensity separately apart from the zone of plate surface 1/5 on the thickness of slab direction are more than (211).
<secondary recrystallization temperature measuring >
Then, with 1600 ℃～2200 ℃, embodiment 1 and resulting each test portion of comparative example 1 are carried out to the thermal treatment of 1 hour～the longest 10 hours in hydrogen stream, TD face (with reference to Fig. 1) to the sheet material after thermal treatment carries out structure observation, utilize above-mentioned segment method to calculate the average crystalline particle diameter, the secondary recrystallization temperature is estimated.
It should be noted that, by embodiment 1 and resulting each test portion of comparative example 1, during reaching above-mentioned each temperature, primary recrystallization occurs, particularly at 1000 ℃～1100 ℃, primary recrystallization occurs.
In the mensuration of average crystal grain, the TD face of Fig. 1 is carried out to structure observation, and calculate crystal particle diameter.For test film, on sheet material separately, by length, be that 30mm cuts, be adjusted to and can observe grain-size by grinding/etching, and calculate crystal particle diameter by segment method.More specifically, as shown in Figure 3,1 test film is drawn to 3 parallel lines arbitrarily in the sheet material top and bottom, calculate the crystal particle diameter on line separately, the average crystalline particle diameter using its mean value as this test portion.
But the crystal particle diameter after secondary recrystallization is more than 1mm, tissue morphology is the tissue morphology shown in the mode chart of Fig. 4 C, so sometimes be difficult to the particular crystal particle diameter.Therefore, if the above crystal particle diameter of 15mm all is expressed as " more than 15mm ".The results are shown in Fig. 7.
Obviously known according to Fig. 7: for the test portion of embodiment 1, to TD face all zones, carry out more than 1700 ℃ and the heating of at least 10 hours, so crystal particle diameter is more than 15mm, on the other hand, test portion for comparative example 1, in the situation that only thickness of slab is 1.0mm, by the thermal treatment at 2000 ℃, gigantism is to more than 15mm, if other test portions of comparative example 1 do not carry out the heating of 2200 ℃, can't not obtain the above crystal grain of 15mm.In addition, under 1600 ℃ of conditions, in embodiment 1 and comparative example 1, the average crystalline particle diameter is below 100 μ m, and secondary recrystallization does not occur.It should be noted that, on any 3 lines that the average crystalline particle diameter is measured without significant difference.The crystalline structure that secondary recrystallization occurs is similar to the form meaned with mode chart in the C of Fig. 4.
In addition, for the test portion of embodiment 1, in the mensuration of the crystal particle diameter in molybdenum board material cross section, the TD face is observed, but also obtained same tissue on the RD face.
In patent documentation 1, the rolling condition of molybdenum board material and crystal face etc. are not described; but contrast this result, can think that the present embodiment puts down in writing pass through 2200 ℃ heated and with the whole comparative example 1 that independently makes the huge granulation of crystal grain heat-up time be the sheet material that roughly meets patent documentation 1.That is, knownly with the similar product of patent documentation 1, compare, the test portion of embodiment 1 has carried out huge crystallization at low temperature.
<anti-creep properties evaluation >
Then, with the deflection of the load test based on 1800 ℃, the anti-creep properties of the test portion of embodiment 1 and comparative example 1 is estimated.
Particularly, at first, in hydrogen stream, with 1800 ℃ of test films to embodiment 1, carry out heating in 5 hours, make its secondary recrystallization, and be processed into and be of a size of wide 20mm * long 150mm.It should be noted that, used the sheet material of thickness of slab for 1.0mm, 1.5mm, 2.0mm, 3.0mm, 10mm, 20mm.The test film of comparative example 1 carries out similarly heat treated and is processed into the size of regulation.Secondary recrystallization does not all occur in each test portion of comparative example 1.
Then, as shown in Figure 8, test film 1 is arranged on tungsten fixture 2 processed and 2 '.Fixture 2 and 2 ' distance are 100mm, and the central part of the test film on fixture 2 and 2 ' is applied to loading 3.Loading during for test, when when when during thickness of slab 1mm, loading is 125g, thickness of slab 1.5mm, loading is 280g, thickness of slab 2mm, loading is 500g, thickness of slab 3mm, loading is 1.1kg.In addition, consider the security of test, the loading at the trial of the sheet material of thickness of slab 10mm and 20mm is 12.5kg.
Then, test film is being applied under the state of described loading, in hydrogen stream, take 1800 ℃ grow most as the heating of 100 hours, measure the deflection of test portion.As shown in Figure 8, deflection means with the difference of the position of the upper surface of the test film 1 before testing and the test film 1 ' after test, uses microcomputer (Micro gauge) to measure.It should be noted that, consider the security of test, the sample that the 20mm distortion occurs is in this abort constantly, do not carry out the test of heat-up time under condition of longer time.
The deflection of measuring is shown in Fig. 9.It should be noted that, " the stopping " in figure refers to the abort because deflection reaches 20mm.
As shown in Figure 9, irrelevant with thickness of slab, the 20mm distortion was occurring in the test portion of comparative example 1 after 20 hours, and the test portion of embodiment 1 does not illustrate good anti-creep properties almost deforming after 100 hours.In addition, put down in writing the data of the thickness of slab 2mm that utilizes same test method and obtain in the patent documentation 1 as prior art, compared with this test-results, product of the present invention have obtained equal above excellent results.
(comparative example 2)
To sheet material that in the sheet material of embodiment 1, thickness of slab is 1.5mm by grinding from two surface removals until to the zone of the 1/5+50 μ m of the degree of depth, in hydrogen stream with 1600 ℃～2200 ℃ thermal treatments of carrying out 1 hour to the longest 10 hours, TD face (with reference to Fig. 1) to the test portion after thermal treatment carries out structure observation, calculate the average crystalline particle diameter by above-mentioned segment method, the secondary recrystallization temperature is estimated.
Consequently: the same with the test portion of comparative example 1, if above-mentioned sheet material is not heat-treated to 2200 ℃, can not produce the gigantism of the crystal grain that secondary recrystallization causes.
It is believed that this be due to: for the test portion of embodiment 1, apart from the zone of two case depths 1/5, formed the core that produces the starting point of secondary recrystallization in the temperature lower than in the past.
Known according to above result: at least 1 face of the opposite face up and down of molybdenum board material along the thickness of slab direction apart from during surface is equivalent to the zone of 1/5th degree of depth arbitrarily, to relative rolling direction, the peak intensity of the crystalline diffraction face of parallel face is controlled, can obtain thus the molybdenum board material with industrialness advantage as described below, with conventional art (patent documentation 1), compare, can produce secondary recrystallization in lower temperature, and anti-creep properties excellence.
Industrial applicibility
Above, based on embodiment and embodiment, describe the present invention, but the present invention is not limited to above-mentioned embodiment.
To those skilled in the art, expect that within the scope of the invention various variation or improvement example are natural, it can be understood these and also belong to scope of the present invention.
For example, process to make molybdenum board material by rolling in above-mentioned embodiment and embodiment, but can be also the molybdenum board material obtained by Forgingother processing etc., control as long as carry out the peak of embodiment and the described X-ray diffraction face of embodiment, similarly can make its secondary recrystallization.
In addition, in above-mentioned embodiment and embodiment, using the tabular shape as molybdenum, even but the shape beyond the sheet material of line clavate shape for example, the recrystallize phenomenon is also essentially identical, if therefore think as the above-mentioned peak control of carrying out the X-ray diffraction face, similarly can make it at the low temperature secondary recrystallization.In such situation, as long as the peak intensity of X-ray diffraction face in zone of 1/5th degree of depth that the rod surface is equivalent to the diameter of line rod along central shaft apart from line meets above-mentioned condition.
It should be noted that, the present invention is for high-temperature structural material and component materials, especially for the wall that forms High Temperature Furnaces Heating Apparatus or support the parts of other constituent materials, more specifically, backing plate is used in firing of being used for the material of the formation High Temperature Furnaces Heating Apparatus main bodys such as platen, well heater, reflector or the fastening piece as bolt or while manufacturing the sintered compact such as pottery, MIM (metal injection molded) product and rare earth element magnet.
In addition, the present invention can be as the parts of stove for single crystal growing, the parts of the formation stove of stove for the single crystal growing when particularly for example aluminium being carried out melting and manufactures sapphire single-crystal; Or also as because the distortion after secondary recrystallization is less and for the parts of the sapphire single-crystal that stretches.
Nomenclature
Test film before 1 creep test
Test film after 1 ' creep test
2,2 ' creep test fixture
3 creep test loadings.
Claims (8)
1. a Mo, it is characterized in that, along thickness direction apart from surface, be equivalent in the zone of 1/5th the degree of depth of total thickness, at least a portion has part as described below: carry out in the situation of X-ray diffraction mensuration, this part has the zone that crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
2. Mo as claimed in claim 1, is characterized in that, molybdenum content is more than 98.0 quality %.
3. as claim 1 or the described Mo of 2 any one, it is characterized in that, this Mo has the sheet material shape, in the zone of 1/5th the degree of depth that is equivalent to thickness of slab along the thickness of slab direction apart from surface of at least 1 face of the opposite face up and down of sheet material, at least a portion has part as described below: carry out in the situation of X-ray diffraction mensuration, this part has the zone that crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
4. as claim 1 or the described Mo of 2 any one, it is characterized in that, this Mo has line clavate shape, along central axis direction apart from surface, be equivalent in the zone of 1/5th the degree of depth of diameter, at least a portion has part as described below: carry out in the situation of X-ray diffraction mensuration, this part has the zone that crystalline diffraction face (110) and (220) peak intensity separately are less than the peak intensity of (211).
5. Mo as described as claim 1～4 any one, is characterized in that, when the temperature more than 1700 ℃ has been carried out thermal treatment, the median size based on segment method of the crystal grain in this Mo cross section is more than 15mm.
6. a Mo, is characterized in that, this Mo is in the temperature more than 1700 ℃, the described Mo of claim 1～5 any one to be heat-treated and obtained, and the median size based on segment method of the crystal grain in described cross section is more than 15mm.
7. a process furnace structure unit, is characterized in that, this process furnace has the described Mo of claim 1～6 any one with structure unit.
8. fire and use backing plate for one kind, it is characterized in that, this is fired with backing plate has Mo claimed in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-068071 | 2011-03-25 | ||
| JP2011068071A JP5160660B2 (en) | 2011-03-25 | 2011-03-25 | Molybdenum material |
| PCT/JP2012/050325 WO2012132489A1 (en) | 2011-03-25 | 2012-01-11 | Molybdenum material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103459631A true CN103459631A (en) | 2013-12-18 |
| CN103459631B CN103459631B (en) | 2016-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201280014329.2A Active CN103459631B (en) | 2011-03-25 | 2012-01-11 | Mo |
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| Country | Link |
|---|---|
| US (1) | US20140014235A1 (en) |
| EP (1) | EP2690185A4 (en) |
| JP (1) | JP5160660B2 (en) |
| KR (1) | KR101587837B1 (en) |
| CN (1) | CN103459631B (en) |
| WO (1) | WO2012132489A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106574324A (en) * | 2014-08-20 | 2017-04-19 | 攀时奥地利公司 | Metallization for a thin film component, method for the production thereof, and sputtering target |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180244535A1 (en) | 2017-02-24 | 2018-08-30 | BWXT Isotope Technology Group, Inc. | Titanium-molybdate and method for making the same |
| CN108145157B (en) * | 2017-12-25 | 2020-03-27 | 安泰天龙钨钼科技有限公司 | Preparation method of high-performance molybdenum-rhenium alloy bar |
| CN114669620A (en) * | 2022-03-08 | 2022-06-28 | 成都联虹钼业有限公司 | Sintering-bearing molybdenum plate for precision ceramic sintering and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140615A (en) * | 1991-04-23 | 1993-06-08 | Toho Kinzoku Kk | Heat-resistant molybdenum plate |
| JPH06158252A (en) * | 1992-11-18 | 1994-06-07 | Toshiba Corp | High formability molybdenum plate and manufacture thereof and reflecting sheet |
| JP2007113033A (en) * | 2005-10-18 | 2007-05-10 | Hitachi Metals Ltd | METHOD FOR PRODUCING Mo TARGET MATERIAL, AND Mo TARGET MATERIAL |
| CN101503775A (en) * | 2009-03-20 | 2009-08-12 | 中南大学 | Composite nano microparticle strongly toughened sintering molybdenum material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61143548A (en) * | 1984-12-14 | 1986-07-01 | Tokyo Tungsten Co Ltd | Molybdenum material |
| AT389326B (en) * | 1987-11-09 | 1989-11-27 | Plansee Metallwerk | METHOD FOR PRODUCING SEMI-FINISHED PRODUCTS FROM Sintered Refractory Metal Alloys |
| JPH0754093A (en) * | 1993-08-10 | 1995-02-28 | Tokyo Tungsten Co Ltd | Molybdenum material and production thereof |
| JP3917208B2 (en) * | 1996-01-19 | 2007-05-23 | 株式会社アライドマテリアル | Tungsten-molybdenum alloy crucible and method for producing the same |
| JPH1072602A (en) * | 1996-09-02 | 1998-03-17 | Nippon Tungsten Co Ltd | Production of sheet material having high thermal conductivity |
| US20100108501A1 (en) * | 2007-01-12 | 2010-05-06 | Nippon Steel Materials Co., Ltd | Mo-based sputtering target plate and method for manufacturing the same |
-
2011
- 2011-03-25 JP JP2011068071A patent/JP5160660B2/en active Active
-
2012
- 2012-01-11 WO PCT/JP2012/050325 patent/WO2012132489A1/en active Application Filing
- 2012-01-11 US US14/007,129 patent/US20140014235A1/en not_active Abandoned
- 2012-01-11 EP EP12765740.1A patent/EP2690185A4/en not_active Ceased
- 2012-01-11 CN CN201280014329.2A patent/CN103459631B/en active Active
- 2012-01-11 KR KR1020137028078A patent/KR101587837B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05140615A (en) * | 1991-04-23 | 1993-06-08 | Toho Kinzoku Kk | Heat-resistant molybdenum plate |
| JPH06158252A (en) * | 1992-11-18 | 1994-06-07 | Toshiba Corp | High formability molybdenum plate and manufacture thereof and reflecting sheet |
| JP2007113033A (en) * | 2005-10-18 | 2007-05-10 | Hitachi Metals Ltd | METHOD FOR PRODUCING Mo TARGET MATERIAL, AND Mo TARGET MATERIAL |
| CN101503775A (en) * | 2009-03-20 | 2009-08-12 | 中南大学 | Composite nano microparticle strongly toughened sintering molybdenum material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106574324A (en) * | 2014-08-20 | 2017-04-19 | 攀时奥地利公司 | Metallization for a thin film component, method for the production thereof, and sputtering target |
| US11047038B2 (en) | 2014-08-20 | 2021-06-29 | Plansee Se | Metallization for a thin-film component, process for the production thereof and sputtering target |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012132489A1 (en) | 2012-10-04 |
| CN103459631B (en) | 2016-06-08 |
| US20140014235A1 (en) | 2014-01-16 |
| KR20140002010A (en) | 2014-01-07 |
| EP2690185A4 (en) | 2014-12-24 |
| JP2012201930A (en) | 2012-10-22 |
| KR101587837B1 (en) | 2016-01-22 |
| EP2690185A1 (en) | 2014-01-29 |
| JP5160660B2 (en) | 2013-03-13 |
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