WO2014148211A1 - チタン板 - Google Patents

チタン板 Download PDF

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Publication number
WO2014148211A1
WO2014148211A1 PCT/JP2014/054550 JP2014054550W WO2014148211A1 WO 2014148211 A1 WO2014148211 A1 WO 2014148211A1 JP 2014054550 W JP2014054550 W JP 2014054550W WO 2014148211 A1 WO2014148211 A1 WO 2014148211A1
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Prior art keywords
titanium plate
mass
crystal grain
titanium
concentration
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PCT/JP2014/054550
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English (en)
French (fr)
Japanese (ja)
Inventor
松本　克史
良規 伊藤
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株式会社神戸製鋼所
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Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to KR1020157025191A priority Critical patent/KR101743380B1/ko
Priority to CN201480015891.6A priority patent/CN105308199B/zh
Priority to US14/764,738 priority patent/US20150376738A1/en
Publication of WO2014148211A1 publication Critical patent/WO2014148211A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
    • F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
    • F28F21/081—Heat exchange elements made from metals or metal alloys
    • F28F21/086—Heat exchange elements made from metals or metal alloys from titanium or titanium alloys
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F3/00—Plate-like or laminated elements; Assemblies of plate-like or laminated elements
    • F28F3/02—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations
    • F28F3/04—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations the means being integral with the element
    • F28F3/042—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations the means being integral with the element in the form of local deformations of the element
    • F28F3/046—Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations the means being integral with the element in the form of local deformations of the element the deformations being linear, e.g. corrugations

Definitions

  • the present invention relates to a titanium plate having both high strength and high formability.
  • titanium materials are excellent in specific strength and corrosion resistance. Taking advantage of this property, titanium materials are used for optical equipment such as camera bodies, exterior materials such as home appliances, materials for accessories such as glasses and watches, civilian parts such as kitchen equipment, and transportation equipment such as motorcycles and automobiles. It has been used as a member and a member of a heat exchanger of a plant such as chemical, electric power and food production. Of these, heat exchangers that have been increasingly used in recent years, especially plates of plate heat exchangers, are processed into corrugations by press molding to increase the surface area in order to increase the heat exchange efficiency required as a required characteristic. Is required. Therefore, a titanium plate applied to a heat exchanger, particularly a plate of a plate heat exchanger, is required to have excellent formability in order to have a deeper wave.
  • Titanium plates frequently used for these are defined in JIS standard JIS H4600 (established July 1, 1964). Titanium plates specified here are further classified into 1 type, 2 types, 3 types, etc. according to the amount of impurities such as Fe and O, strength, etc. The minimum strength of the titanium plate increases as the grade increases. It is high. The titanium plate is properly used according to the application according to the JIS standard grade. Like JIS type 1, a titanium plate having a low concentration of Fe and O has low ductility but high strength. For this reason, conventionally, a JIS type 1 pure titanium plate has been used for members that require high formability.
  • regulated by JIS specification is a metal material mainly comprised by the crystal grain structure of the alpha phase which consists of a hexagonal crystal (HCP) structure.
  • HCP hexagonal crystal
  • slip deformation due to dislocation movement and plastic deformation including twin deformation are required.
  • a slip system that easily acts in the ⁇ phase of titanium is a column surface slip ⁇ 10-10 ⁇ ⁇ 11-20>, and a bottom surface slip ⁇ 0001 ⁇ ⁇ 11-20> and a weight surface slip.
  • ⁇ 11-22 ⁇ ⁇ 11-23> twins can be active during deformation during press molding.
  • titanium has a smaller number of active slip systems than a steel material having a BCC structure and aluminum having an FCC structure, and a plurality of slip systems are not easily activated. For this reason, it is known that plastic deformation of titanium is difficult.
  • the strength is mainly improved by increasing the concentration of impurity elements such as O and Fe of the titanium material, or by improving the grain size of the titanium material.
  • impurity elements such as O and Fe of the titanium material
  • Two means are known.
  • increasing the strength of the titanium material by these conventional methods has a problem that the formability of the titanium material is greatly reduced.
  • Patent Document 1 a pure titanium material in which the content ratios of Fe, Ni, and Cr satisfy a predetermined relational expression in terms of weight ratio, the O (oxygen) content is 900 ppm or less, and the balance is Ti and inevitable impurities. Then, it is cold-rolled and then annealed at a temperature of 600 to 850 ° C. so that the average crystal grain size of the pure titanium plate is 20 to 80 ⁇ m, and then pickled with an aqueous solution of nitric hydrofluoric acid that satisfies a predetermined relational expression. A method of manufacturing a pure titanium plate characterized by performing a treatment has been proposed.
  • the amount of H, O, N, and Fe is an amount defined by one or two of JIS H 4600, C: a composition containing 50 to 800 ppm, and the balance comprising titanium and inevitable impurities
  • JIS H 4600, C a composition containing 50 to 800 ppm, and the balance comprising titanium and inevitable impurities
  • the present invention has been made in view of the above problems, and an object thereof is to provide a titanium plate having both strength and formability.
  • the ductility of the titanium plate is further improved by precisely controlling the addition amount of Fe, O, and C with respect to the improvement of the ductility of the titanium plate, which is limited by the conventional C and Al composite content. Further, it has also been found that the distribution state of C to the crystal grain boundary influences the effect of improving ductility. And it discovered that the ductility of a titanium plate improved further by controlling precisely the concentration degree of C to a crystal grain boundary.
  • the strength of the titanium plate increases.
  • the effect of the C content can be obtained in the optimum range where the C content of the titanium plate is present.
  • the optimum range also depends on the amounts of Fe and O added.
  • O has a great effect of increasing the strength of the titanium plate, but also deteriorates the ductility of the titanium plate.
  • the amount of O addition is small.
  • Fe it has been found that a larger amount of addition is more effective in improving the balance between the strength and formability of the titanium plate when C is contained.
  • the present inventors have found that the balance between strength and ductility increases even with the same addition amount as the concentration degree at the crystal grain boundary is higher as the location of C in the crystal grain structure of the titanium plate.
  • the present inventors have intensively studied, and by controlling the content of Fe, O, and C, and the ratio of each other, the balance between the strength and formability of the titanium plate is improved. It has been found that the formability of the titanium plate is further improved by increasing the degree of concentration of C to the crystal grain boundary, leading to the present invention.
  • the titanium plate according to the present invention is a titanium plate having a crystal grain structure which is an ⁇ phase, Fe: 0.020 to 0.150 mass%, O: 0.020 to 0.150 mass%, C: 0 0.002 to 0.100% by mass, the balance being titanium and inevitable impurities, the sum of the content of Fe and C (% by mass) being 0.80 times the content of O (% by mass)
  • the C concentration in the crystal grain boundary is 1.0% by mass or more.
  • the titanium plate has the strength and formability of the titanium plate by controlling the content of Fe, O, and C and the ratio of each other to activate a plurality of slip systems / twin systems.
  • the balance is improved.
  • the moldability of a titanium plate further improves by making the density
  • the titanium plate according to the present invention preferably has an average crystal grain size of 5 to 80 ⁇ m.
  • the titanium plate is more likely to undergo dislocation slip deformation and twinning deformation while securing the strength of the titanium plate during molding. For this reason, the moldability of the titanium plate is further improved.
  • the titanium plate of the present invention can be used for a plate-type heat exchanger.
  • a plate heat exchanger having high strength and high formability can be obtained.
  • the titanium plate according to the present invention has both strength and formability by defining the predetermined composition and the concentration of C at the grain boundaries.
  • (A) is a top view of the shaping
  • (B) is sectional drawing in the EE line of a shaping die.
  • the titanium plate according to the present invention has a crystal grain structure of ⁇ phase (HCP structure), Fe: 0.020 to 0.150 mass%, O: 0.020 to 0.150 mass%, C: 0.00. 002 to 0.100% by mass, the balance is titanium and inevitable impurities, and the sum of Fe and C content (% by mass) is 0.80 times or more O content (% by mass) .
  • the C concentration at the crystal grain boundary is 1.0 mass% or more.
  • Fe 0.020 to 0.150 mass%
  • Fe is an important element that improves the strength and formability of the titanium plate.
  • the Fe content is set to 0.020% by mass or more.
  • the Fe content is set to 0.100% by mass or less.
  • the Fe content is more preferably 0.080% by mass or less.
  • O is an element that increases the strength of the titanium plate while degrading formability.
  • strength of a titanium plate will become it low that content of O is less than 0.020 mass%. Therefore, the amount of strain to be introduced in order to increase the strength of the titanium plate increases, and as a result, the formability of the titanium plate decreases. Therefore, the content of O is set to 0.020% by mass or more.
  • the content of O exceeds 0.150% by mass, the titanium plate becomes brittle and the formability is lowered. Further, the titanium plate is easily broken during cold rolling, and the productivity of the titanium plate is lowered. Therefore, the O content is 0.150% by mass or less.
  • the content of O is preferably 0.125% by mass or less.
  • the content of O is more preferably 0.100% by mass or less.
  • C (C: 0.002 to 0.100 mass%) C is an element that improves the strength and formability of the titanium plate. If the C content is less than 0.002% by mass, it becomes difficult to make the C concentration at the crystal grain boundary a predetermined concentration, and the effect of improving the balance between the strength and formability of the titanium plate cannot be obtained. Further, the strength of the titanium plate is lowered. Accordingly, the C content is set to 0.002% by mass or more. On the other hand, when the content of C exceeds 0.100 mass%, the strength of the titanium plate increases more than necessary, and the formability of the titanium plate deteriorates. Therefore, the C content is 0.100% by mass or less. The content of C is preferably 0.090% by mass or less. The content of C is more preferably 0.080% by mass or less.
  • the inevitable impurities in the titanium plate according to the present invention refer to impurity elements inevitably contained in the industrial pure titanium plate.
  • the impurity element typically includes nitrogen, hydrogen, chromium, nickel, and the like.
  • elements that may be incorporated into the product in the manufacturing process, such as hydrogen, are also included in the inevitable impurities.
  • the impurity content is large, it becomes difficult for the titanium plate to have both strength and formability. For this reason, it is desirable that the titanium plate has an inevitable reduction of inevitable impurities.
  • the inevitable impurity of a titanium plate can be reduced by using an alloy raw material with few impurities.
  • composition index R 0.80 or more
  • the content of Fe, O, and C is a composition index R represented by the following formula (1) when the content (% by mass) in the titanium plate is expressed as [Fe], [C], and [O]. Can be expressed as 0.80 or more.
  • the composition index R is controlled by adding Fe, for example, iron powder, O, for example, titanium oxide, and C, for example, TiC as appropriate to the Fe, O, and C concentrations contained in the titanium scrap used as the raw material for the titanium plate. And it controls by controlling Fe, O, and C content in a titanium plate.
  • the strength of the titanium plate increases as the C content increases.
  • the effect of the ductility of the titanium plate is obtained in an optimum range with a C content.
  • the optimum range of the C content also depends on the Fe and O contents.
  • O has a great effect of increasing the strength of the titanium plate.
  • O deteriorates the ductility of the titanium plate. For this reason, in order to express the effect of C content more efficiently, the smaller the O content, the better. Further, in order to more efficiently express the improvement of the balance between the strength and formability of the titanium plate due to C, the higher the Fe content, the more effective.
  • the lower limit value of the composition index R is 0.80 or more.
  • the value of the composition index R is 0.80 or more, a plurality of slip systems / twin systems can be activated, and the balance between the strength and formability of the titanium plate is improved.
  • the value of the composition index R is preferably 0.85 or more.
  • the value of the composition index R is more preferably 0.90 or more. If the value of the composition index R is less than 0.80, a plurality of slip systems / twin systems cannot be activated, and the formability of the titanium plate is inferior.
  • the upper limit of the composition index R is preferably 12.5 or less in the range of the contents of Fe, O, and C. If the value of the composition index R exceeds 12.5, the content of any element of Fe, O, and C deviates from the preferred range, so the balance between the strength and formability of the titanium plate is the value of the composition index R. Is inferior to the case of 12.5 or less. More preferably, the value of the composition index R is 10.0 or less. More preferably, the value of the composition index R is 6.0 or less.
  • concentration state of C at the crystal grain boundary affects the effect of improving the ductility of the titanium plate.
  • concentration state of C to the crystal grain boundary affects the effect of improving the ductility of the titanium plate.
  • concentration of C in a crystal grain boundary affects the effect of improving the ductility of the titanium plate.
  • concentration of C in a crystal grain boundary affects the effect of improving the ductility of the titanium plate.
  • concentration of C in a crystal grain boundary concentration of C to a crystal grain boundary
  • concentration of C to a crystal grain boundary concentration of C to a crystal grain boundary
  • the balance between the strength and formability of the titanium plate is better than in the case of other measures to increase strength (O increase, crystal grain refinement, prestraining). improves.
  • the concentration of C at the crystal grain boundary is 1.0 mass% or more.
  • the concentration of C at the crystal grain boundary is preferably 2.0% by mass or more.
  • concentration of C in a crystal grain boundary 5.0 mass% or more is more preferable.
  • Control of the C concentration at the crystal grain boundary is performed by a manufacturing method described later. Specifically, it is performed by controlling the cold rolling rate in the cold rolling process before the final annealing. Moreover, it controls by controlling the annealing temperature and annealing time in the final annealing process.
  • the cold rolling rate in the cold rolling step before the final annealing is lowered, C tends to be actively concentrated (distributed) at the grain boundaries.
  • the annealing temperature in the final annealing process is high, C is actively concentrated at the grain boundaries.
  • the annealing time in the final annealing process is long, C is actively concentrated at the grain boundaries.
  • C is an interstitial element and therefore exists in a solid solution state within the range of the present invention.
  • concentration degree distributed concentration
  • the Ti crystal grain boundary As the location of C, the better the balance between the strength and formability of the titanium plate, even if the content in the entire titanium plate is the same.
  • this mechanism is unknown, it is guessed as follows.
  • strain concentration occurs at the Ti grain boundary due to twins and deformation structures formed by the progress of plastic deformation, leading to fracture.
  • strength of Ti crystal grain boundary increases when C segregates to a crystal grain boundary, and the strain concentration to a specific crystal grain boundary becomes difficult to occur. As a result, it is assumed that the balance between the strength and formability of the titanium plate is improved.
  • the average crystal grain size affects the formability of the titanium plate, but the effect of the present invention is exhibited as long as the average crystal grain size is within the range of the normal average crystal grain size (2 to 150 ⁇ m) in the titanium plate according to the present invention. If the average crystal grain size is within the range of the normal average crystal grain size and the average crystal grain size is less than 5 ⁇ m, twin deformation is less likely to occur when strain is introduced into the titanium plate. In any case, the formability of the titanium plate is slightly lowered. Therefore, the average crystal grain size is preferably 5 to 80 ⁇ m. If the average crystal grain size is 5 to 80 ⁇ m, the moldability is better than that outside the range, so that the moldability index F described later has a higher value. The average crystal grain size is more preferably 10 to 60 ⁇ m.
  • the average crystal grain size is controlled by the production method described later. Specifically, it is performed by controlling the cold rolling rate before the final annealing step, the annealing temperature and the annealing time in the final annealing step.
  • the cold rolling rate before the final annealing step is lowered, the average crystal grain size is increased.
  • the annealing temperature in the final annealing process is high, the average crystal grain size becomes large.
  • T ⁇ ⁇ transformation temperature
  • the growth of crystal grains is inhibited by the newly precipitated ⁇ phase.
  • the annealing time in the final annealing process is long, the average crystal grain size becomes large.
  • the average crystal grain size can be measured, for example, by subjecting an observation structure of a scanning electron microscope (SEM: Scanning Electron Microscopy) to orientation analysis using an EBSD (Electron Back Scattered Diffraction Pattern).
  • SEM Scanning Electron Microscopy
  • EBSD Electro Back Scattered Diffraction Pattern
  • a sample is irradiated with an electron beam, and the crystal orientation is specified by using reflected electron Kikuchi diffraction that occurs at that time.
  • the average crystal grain diameter is a diameter when a boundary having an orientation difference of 5 ° or more is defined as a crystal grain boundary, and the area of each crystal grain surrounded by the crystal grain boundary is approximated to a circle.
  • the average value of equivalent circle diameters is calculated for 100 or more crystal grains used for the calculation, and the average value of each equivalent circle equivalent diameter calculated by performing the same measurement at a plurality of locations (5 locations or more) is calculated. And define it as the average grain size.
  • the plate for a plate-type heat exchanger according to the present invention is obtained by processing the titanium plate according to the present invention into a predetermined shape such as a deep corrugated shape by a known method such as press working.
  • the titanium plate according to the present invention has both strength and formability due to the chemical composition already described and the distribution state of C to the crystal grain boundaries. For this reason, the titanium plate according to the present invention is excellent in formability without causing cracks or the like even if the plate heat exchanger plate is processed to have a deep wave at the time of processing.
  • the plate for heat exchangers according to the present invention since the plate for heat exchangers according to the present invention has strength, it can withstand the severe use environment of the heat exchanger for a long time.
  • the titanium plate according to the present invention is produced by a conventional manufacturing method (consuming electrode arc melting method (VAR method) melting step, remelting step, casting step, hot forging step, hot rolling step, intermediate annealing step, cold Rolling process, final annealing process).
  • VAR method consuming electrode arc melting method
  • a method for controlling the concentration of C at the crystal grain boundary in the production process of the titanium plate according to the present invention is as follows.
  • Cold rolling process In the cold rolling process, an appropriate rolling reduction and annealing conditions are selected according to the cold rolling properties of the material (ease of occurrence of ear cracks, deformation load, etc.), and cold rolling and annealing are repeated.
  • the rolling reduction of the cold rolling performed immediately before the final annealing step ensures a reduction amount sufficient to recrystallize the material in the final annealing step, for example, a rolling reduction of 30% or more.
  • the cold rolling rate in the cold rolling step before final annealing is preferably 85% or less. This condition suppresses the development of the recrystallized texture after the final annealing, reduces the proportion of low-angle grain boundaries where C concentration is difficult, and increases the proportion of large-angle grain boundaries where C is likely to concentrate. To do.
  • the cold rolling rate should be low, and more preferably 70% or less.
  • the cold rolling rate is more preferably 60% or less.
  • C is actively concentrated at the grain boundaries by promoting the diffusion of C during annealing.
  • the final annealing conditions are preferably high temperature and long time.
  • the annealing temperature for the final annealing in the continuous annealing furnace is preferably 600 to 890 ° C.
  • the annealing temperature for the final annealing in the continuous annealing furnace is more preferably 700 to 890 ° C.
  • Holding is not essential in the final annealing in the continuous annealing furnace (may be 0 minutes), but when holding, the holding time is preferably 10 minutes or less.
  • the holding time exceeds 10 minutes, the grain growth remarkably follows recrystallization that occurs during annealing, and the degree of accumulation in a specific orientation increases. For this reason, the ratio of the low-angle grain boundaries in which it is difficult to concentrate C increases, making it difficult for C to concentrate on the crystal grain boundaries.
  • the concentration of C at the crystal grain boundaries is 1.0% by mass or more. It ’s hard to be.
  • the holding time of the final annealing by the continuous annealing furnace is more preferably 1 minute to 10 minutes.
  • the annealing temperature for the final annealing in the batch annealing furnace is preferably 550 to 700 ° C.
  • the annealing temperature is less than 550 ° C., C does not sufficiently concentrate on the crystal grain boundary, so the C concentration at the crystal grain boundary does not become 1.0 mass% or more.
  • the annealing temperature exceeds 700 ° C., grain growth is remarkably generated following recrystallization that occurs during annealing, and the degree of accumulation in a specific orientation increases. For this reason, the ratio of the low-angle grain boundaries in which it is difficult to concentrate C increases, making it difficult for C to concentrate on the crystal grain boundaries.
  • the concentration of C at the crystal grain boundaries is 1.0% by mass or more. It ’s hard to be.
  • the annealing temperature of the final annealing using a batch annealing furnace is more preferably 600 to 700 ° C.
  • the holding time of the final annealing by the batch annealing furnace is preferably 30 minutes to 4 hours. If the holding time is less than 30 minutes, the concentration of C at the crystal grain boundary does not sufficiently occur, so the C concentration at the crystal grain boundary does not become 1.0 mass% or more. When the holding time exceeds 4 hours, the grain growth remarkably follows the recrystallization that occurs during annealing, and the degree of accumulation in a specific orientation increases. For this reason, the ratio of the low-angle grain boundaries in which it is difficult to concentrate C increases, making it difficult for C to concentrate on the crystal grain boundaries.
  • the concentration of C at the crystal grain boundaries is 1.0% by mass or more. It ’s hard to be.
  • the holding time for the final annealing in the batch annealing furnace is more preferably 1 to 4 hours.
  • it is preferable to perform the process of scale removal for example, salt heat processing, a pickling process, etc.
  • Test material It melt
  • this titanium material was hot forged at 1000 ° C. for 30 minutes and then hot rolled at 800 ° C. to obtain a hot rolled sheet having a thickness of 4.0 mm.
  • cold rolling and intermediate annealing 750 degreeC x 5 minutes with a continuous annealing furnace
  • it was immersed in a salt furnace, and then pickled and descaled.
  • cold rolling and final annealing were performed under the conditions shown in Table 1 to obtain test materials (test material numbers 1 to 27) having a plate thickness of 0.5 mm.
  • Final annealing was performed in a continuous annealing furnace or a batch annealing furnace (vacuum furnace).
  • concentration of C in a crystal grain boundary was 1.0 mass% or more.
  • the steel sheet is immersed in a salt furnace after the final annealing, and then pickled and descaled so that the sheet thickness is 0.5 mm before and after the intermediate annealing. Adjusted.
  • Evaluation of the concentration of C at the grain boundary was performed by a field emission transmission electron microscope (FE-TEM) and an energy dispersive X-ray spectrometer (EDX) using an energy dispersive X-ray spectrometer (EDX).
  • FE-TEM field emission transmission electron microscope
  • EDX energy dispersive X-ray spectrometer
  • JEM-2010F FE-TEM
  • EDX energy dispersive X-ray spectrometer
  • the time which irradiated the electron beam for the EDX spectrum measurement was 30 seconds. From the spectrum, the C concentration at the grain boundary was analyzed. For each field of view, the C concentration at the grain boundary was analyzed at 10 locations, and the average value was calculated. Further, for each test material, the above measurement was performed in five fields of view, and the average value thereof was calculated and used as the C concentration at the crystal grain boundary.
  • an observation target is 0.5 mm in the rolling direction and 0.5 mm in the plate width direction on the rolling surface.
  • EBSD Electro Back Scattered Diffraction Pattern, Oxford Instruments, Nordlys II.
  • a boundary having an orientation difference of 5 ° or more was recognized as a grain boundary.
  • the equivalent circle diameter of each crystal grain was calculated.
  • the average equivalent circle diameter was calculated based on the calculated 100 crystal grains. This measurement was performed at any five locations for each portion. Further, the average value of the average equivalent circle diameters at any five locations was calculated to calculate the average crystal grain size.
  • Test strength evaluation A No. 13 test piece defined in JIS Z 2241 (established on July 22, 1952) was collected from the test material in the direction in which the rolling direction of the test material coincided with the load axis. Next, a tensile test was performed at room temperature based on JIS H 4600, and 0.2% yield strength (YS) was measured. A test material having a 0.2% proof stress (YS) of the test piece of 200 MPa or more was accepted.
  • the moldability was evaluated by press molding simulating a plate (heat exchange part) of a plate heat exchanger.
  • the used mold has four twill lines with a molding part of 100 mm ⁇ 100 mm, a pitch of 17 mm, and a maximum height of 6.5 mm. It has an R shape of 2.5.
  • Each twill line portion has a bent portion that is bent in one direction in the middle, is straight from the bent portion to both ends, and is oblique to the edge of the formed portion from the intermediate bent portion to both ends in the formed portion. It is formed to resemble a wave shape.
  • As the press machine an 80-ton press machine (Amino Co., Ltd. universal plastic working machine) was used.
  • the press molding was performed according to the following procedure. First, antirust oil (R303P) was apply
  • antirust oil R303P
  • Formability was determined to be acceptable when the formability index F defined by the following formula (2) is a positive value.
  • the evaluation results are shown in Table 1.
  • F X- (5.972-0.008 ⁇ YS) (2)
  • X depth of indentation YS: 0.2% yield strength
  • Test material numbers 1 to 16 are titanium plates that satisfy all of the requirements (composition, composition index R, crystal grain boundary C concentration) defined in the present invention, and were excellent in balance between strength and press formability.
  • Test Material Nos. 17 to 27 did not satisfy the requirements defined in the present invention, and particularly did not satisfy the requirements for the C concentration at the grain boundaries, the balance between strength and press formability was poor.
  • test material Nos. 17 to 20 the C concentration at the crystal grain boundary was low and the C concentration at the crystal grain boundary was out of the specified range. As a result, the balance between the strength and formability of the titanium plate was poor.
  • the test material numbers 18 to 20 had the following characteristics. In Test Material No. 18, since the C component content specified in the present invention exceeded the range of the present invention, the strength increased more than necessary. In Test Material No. 19, since the Fe component content specified in the present invention exceeds the range of the present invention, the precipitation amount of the ⁇ phase is increased, so that the Ti crystal grains are refined. In Test Material No. 20, the O component content specified in the present invention exceeded the range of the present invention, so that the strength increased more than necessary and became brittle.
  • Test material No. 21 has a high strength because the composition index R is less than the range of the present invention, and the concentration of C at the crystal grain boundary is low and the concentration of C at the crystal grain boundary is less than the specified range. Was brittle and inferior in moldability. Since Test Material No. 22 had a high final cold rolling reduction ratio, the concentration of C at the crystal grain boundary was low, and the C concentration at the crystal grain boundary was less than the specified range, resulting in poor formability.
  • Test material No. 23 had a low annealing temperature for final annealing, a low concentration of C at the crystal grain boundaries, and the C concentration at the crystal grain boundaries was below the specified range, resulting in poor formability.
  • Test material No. 24 had a high annealing temperature in the final annealing, a low concentration of C at the grain boundaries, and the C concentration at the grain boundaries was less than the specified range, resulting in insufficient strength and poor formability.
  • Test Material No. 25 the final annealing time was short, so the annealing was insufficient, the C concentration at the crystal grain boundary was low, and the C concentration at the crystal grain boundary was less than the specified range, resulting in poor formability.
  • Test material No. 26 had a long final annealing time, and the C concentration at the crystal grain boundary was low and the C concentration at the crystal grain boundary was less than the specified range, resulting in poor formability.
  • Test material No. 27 was inferior in formability as a result of excessive annealing due to a long final annealing time, low concentration of C at the crystal grain boundary, and C concentration at the crystal grain boundary being less than the specified range.
  • the titanium plate and the titanium plate manufacturing method according to the present invention have been described in detail with reference to the embodiments and examples.
  • the gist of the present invention is not limited to the above-described contents, and the scope of rights is patented It must be interpreted based on the claims.
  • the content of this invention can be changed or changed based on the above description.
PCT/JP2014/054550 2013-03-19 2014-02-25 チタン板 WO2014148211A1 (ja)

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US14/764,738 US20150376738A1 (en) 2013-03-19 2014-02-25 Titanium sheet

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JP6219199B2 (ja) * 2014-02-27 2017-10-25 株式会社神戸製鋼所 熱交換用プレートとなる元板材、及びその元板材の製造方法
JP6577707B2 (ja) * 2014-11-28 2019-09-18 株式会社神戸製鋼所 チタン板、熱交換器用プレート、燃料電池用セパレータおよびチタン板の製造方法
WO2016152935A1 (ja) * 2015-03-23 2016-09-29 株式会社神戸製鋼所 チタン板、熱交換器用プレートおよび燃料電池用セパレータ
TWI650428B (zh) * 2018-04-10 2019-02-11 日商新日鐵住金股份有限公司 鈦合金及其製造方法
RU2752094C1 (ru) * 2018-04-10 2021-07-22 Ниппон Стил Корпорейшн Титановый сплав и способ его получения
JP7385941B2 (ja) * 2019-08-23 2023-11-24 国立大学法人東京海洋大学 チタン材、該チタン材を加工してなるチタン製品及び該チタン材の製造方法
CN115216667A (zh) * 2022-07-18 2022-10-21 西安秦钛智造科技有限公司 一种金属隔膜用钛板及其加工方法

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JP2005105387A (ja) * 2003-10-01 2005-04-21 Kobe Steel Ltd 表面性状に優れたチタン板
JP2009228092A (ja) * 2008-03-25 2009-10-08 Sumitomo Metal Ind Ltd チタン板ならびにチタン板製造方法
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WO2018003098A1 (ja) * 2016-06-30 2018-01-04 新日鐵住金株式会社 チタン薄板及びその製造方法

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US20150376738A1 (en) 2015-12-31
CN105308199B (zh) 2017-11-24
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JP6263040B2 (ja) 2018-01-17
CN105308199A (zh) 2016-02-03
KR20150119301A (ko) 2015-10-23

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