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WO2010126051A1 - Plaque en titane et procédé de fabrication de plaques en titane - Google Patents

Plaque en titane et procédé de fabrication de plaques en titane Download PDF

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Publication number
WO2010126051A1
WO2010126051A1 PCT/JP2010/057482 JP2010057482W WO2010126051A1 WO 2010126051 A1 WO2010126051 A1 WO 2010126051A1 JP 2010057482 W JP2010057482 W JP 2010057482W WO 2010126051 A1 WO2010126051 A1 WO 2010126051A1
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Prior art keywords
titanium plate
titanium
range
pickling
vickers hardness
Prior art date
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PCT/JP2010/057482
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English (en)
Japanese (ja)
Inventor
良規 伊藤
康宏 林田
義男 逸見
昌吾 村上
翔生 桂
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Kobe Steel Ltd
Original Assignee
Kobe Steel Ltd
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Publication date
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Priority to CN201080016195.9A priority Critical patent/CN102387873B/zh
Publication of WO2010126051A1 publication Critical patent/WO2010126051A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals

Definitions

  • the present invention relates to a titanium plate used for a heat exchanger member, a consumer product such as a camera body and a kitchen device, a transport device member such as a motorcycle and an automobile, and an exterior material such as a home appliance, and a method of manufacturing the titanium plate. .
  • Titanium plates are used in heat exchangers such as chemical, electric power and food production plants because of their excellent corrosion resistance.
  • the plate-type heat exchanger using a titanium plate has improved the heat exchange efficiency by processing the titanium plate into a wave by press molding to increase the surface area. Therefore, such a titanium plate is required to have formability for giving a deep wave. Further, excellent formability is also required when a titanium plate is processed into a camera casing, an exterior product of a household electrical appliance, a member for a transportation device, or the like.
  • the formability requires workability and lubricity of the plate material itself.
  • the titanium plate has a high r value (ratio of logarithmic strain in the plate width direction to logarithmic strain in the plate thickness direction during uniaxial tensile deformation). Further, although the plate material itself has high drawability, since it is an active metal, seizure with a molding die occurs in the molding process. These are factors that lower the forming limit of the titanium plate. For this reason, it is generally said that for molded products that emphasize drawing, it is possible to improve moldability by preventing seizure with a tool, that is, by improving seizure resistance.
  • Patent Document 1 describes a titanium thin plate having a titanium nitride layer with a thickness of 0.1 ⁇ m or more and 1.0 ⁇ m or less on the surface and a nitrogen diffusion layer under the titanium nitride layer.
  • Patent Document 2 describes a titanium thin plate for forming, which has a nitrogen-enriched layer on the surface, and the thickness of the nitrogen-enriched layer is 0.5 ⁇ m or more and 5 ⁇ m or less.
  • Patent Document 3 describes a titanium plate characterized in that a TiC-containing layer is present on the surface layer of the base titanium, and the thickness of the TiC-containing layer is 300 mm or more. In other words, Patent Documents 1 to 3 describe that seizure resistance and formability can be improved by forming a hardened layer on the surface.
  • Patent Document 4 discloses that the surface of a titanium thin plate has a Vickers hardness with a load of 50 gf; HVS0.05 is 180 to 280, a Vickers hardness with a load of 200 gf; HVS0.2 is 170 or less, An industrial pure titanium thin plate characterized in that the Erichsen value based on the above is 11.5 mm or more is described. It is described that the industrial pure titanium thin plate of Patent Document 4 can moderately reduce the surface hardness as compared with the titanium plates of Patent Documents 1 to 3.
  • the arithmetic average roughness of the surface in the direction parallel to the rolling direction is 0.25 ⁇ m or more and 2.5 ⁇ m or less, and the test load is 0.098 N rather than the Vickers hardness due to the test load of 4.9 N on the surface.
  • the titanium plate is characterized in that the Vickers hardness by 20 is higher than 20 and the Vickers hardness by test load 4.9N is 180 or less.
  • the titanium plate of Patent Document 5 prevents the seizure by increasing the amount of lubricant drawn between the titanium plate and the molding die during press molding by increasing the roughness of the surface of the titanium plate to some extent. It is described that seizure flaws after press molding can be reduced.
  • the content ratios of Fe, Ni, and Cr are 100 ppm ⁇ Fe ⁇ 700 ppm, 100 ppm ⁇ Ni + Cr ⁇ 700 ppm, and 200 ppm ⁇ Fe + Ni + Cr ⁇ 1100 ppm by weight ratio, and contain O (oxygen)
  • a pure titanium material having a rate of 900 ppm or less and the balance of Ti and inevitable impurities is subjected to cold rolling, and then annealed at a temperature of 600 to 850 ° C., so that the average grain size of the pure titanium plate is 20 to 80 ⁇ m.
  • Japanese Unexamined Patent Publication No. 10-60620 Japanese Unexamined Patent Publication No. 10-204609 Japanese Unexamined Patent Publication No. 2006-291362 Japanese Patent No. 3600792 Specification Japanese Unexamined Patent Publication No. 2002-3968 Japanese Laid-Open Patent Publication No. 10-30160
  • the titanium plate described in Patent Documents 1 to 3 has a hardened layer formed on the surface, it is preferably applied to products subjected to processing that places importance on seizure resistance.
  • a titanium plate there is a problem that surface molding is liable to occur on the contrary, in molding that places emphasis on overhang molding or bending molding, and the moldability deteriorates.
  • the titanium plate described in Patent Document 4 has a problem that the surface hardness is high and cracking easily occurs, and the surface form is not appropriate and seizure is likely to occur. That is, when it became a severe shape, there existed a problem that generation
  • the titanium plate described in Patent Document 5 is mainly intended to increase the hardness of the surface in order to improve the seizure resistance, there is a problem in that the surface is easily cracked and the formability is deteriorated.
  • this titanium plate improves the oil retaining property during press molding by increasing the surface roughness, but it does not exhibit sufficient oil retaining property because the surface roughness is managed only by Ra. In some cases, it was necessary to form a relatively thick (that is, easily cracked) oxide film in order to prevent seizure. Further, in Patent Document 5, shot blasting is performed as a method for controlling the surface roughness. However, there is a problem in that the titanium plate is easily warped in the subsequent heat treatment, and the correction is required and productivity is poor. It was.
  • the added element inhibits the growth of crystal grains, and a long heat treatment is required to obtain a desired grain size.
  • the moldability itself is poor even when a desired particle size is obtained.
  • the grain boundary parts are preferentially dissolved in the pickling process, so a large number of recesses such as sharp notches are formed along the grain boundaries. It is easy to be done. Therefore, when emphasis is placed on overhang forming or bending forming, there is a problem that cracking is likely to be the starting point, and formability is deteriorated.
  • the present invention has been made based on such a background, and provides a titanium plate having good seizure resistance and crack resistance and exhibiting excellent press formability, and a method for producing the titanium plate. Let it be an issue.
  • the titanium surface In order to make the titanium surface difficult to break, it is effective to remove a hardened layer such as an oxide film.
  • a hardened layer such as an oxide film.
  • the titanium surface from which the hardened layer has been removed is easily seized with the surface of the molding die. When seizure occurs, it becomes the starting point of cracking, and even if it does not develop into cracking, it is necessary to polish the molding die because titanium adheres to the molding die, and productivity decreases. There is a problem. Therefore, it has been a challenge to achieve both removal of the cured layer and seizure resistance.
  • the present inventors have found that the lubrication effect of press oil during press molding can be maximized and seizure resistance can be improved by making the surface irregularities more appropriate. Then, the present inventors have found that it is possible to achieve both the prevention of surface cracking and the prevention of seizure of the titanium plate and the molding die, thereby solving the above-described problems, and completing the present invention. It came.
  • the titanium plate according to the present invention that has solved the above problems has an arithmetic average roughness (Ra) in the range of 0.15 to 1.5 ⁇ m and a maximum height (Rz) of 1.5 to 9.0 ⁇ m.
  • Vickers hardness at a measurement load of 4.9 N is a Vickers hardness at a measurement load of 0.098 N on the surface and a degree of strain (Rsk) in the range of -3.0 to -0.5. The difference is 45 or less.
  • the arithmetic average roughness (Ra) and the maximum height (Rz) are set to a specific numerical value range, it is possible to exhibit oil retention and make it difficult to induce cracking due to the notch effect. it can. Moreover, since it can prevent that the surface pressure to a smooth part raises by making distortion degree (Rsk) into a specific numerical value range, local plastic deformation and seizure can be prevented.
  • the Vickers hardness at the measurement load of 0.098N on the surface is higher than the Vickers hardness at the measurement load of 4.9N, and the difference is set to 45 or less, in other words, the hardened layer is not formed on the surface. By doing so, it is possible to make it difficult for surface cracks to occur during molding.
  • the titanium plate according to the present invention has a crystal grain size in the range of 20 to 80 ⁇ m in average section length when a section cut by a cutting method prescribed in JISJG 0552 is observed with an optical microscope. preferable. If the average intercept length of the crystal grain size is in such a specific numerical range, the unevenness on the surface of the titanium plate is moderately roughened by the pickling process, so that more excellent oil retention can be obtained.
  • the titanium plate according to the present invention preferably has a plate thickness of 1.0 mm or less. With such a plate thickness, it can be suitably used as a member for a heat exchanger.
  • a method for producing a titanium plate according to the present invention includes an atmospheric annealing step in which atmospheric annealing is performed on a titanium plate after cold rolling so that the crystal grain size is 20 to 80 ⁇ m, and after the atmospheric annealing step A pickling step in which the titanium plate is pickled in a pickling bath having a nitric acid / hydrofluoric acid ratio of 1 to 10, and the titanium plate after the pickling step has a rolling reduction of 0.2 to 1.0%.
  • the crystal grain size can be set to a desired size by an atmospheric annealing process performed after cold rolling. Then, by performing the pickling step and skin pass rolling step performed on the titanium plate under specific conditions, the unevenness of the titanium plate surface is in a desired state, that is, a desired arithmetic average roughness (Ra) and maximum height. (Rz) and the degree of distortion (Rsk).
  • the titanium plate according to the present invention can exhibit excellent press formability by having good seizure resistance and crack resistance. Moreover, according to the manufacturing method of the titanium plate which concerns on this invention, the titanium plate which exhibits the outstanding press-formability can be manufactured by having favorable seizure resistance and crack resistance.
  • (A) is a plan view showing the shape of a molding die for evaluating moldability, and (b) is a sectional view taken along line FF in (a).
  • specimen No. 7 is a SEM image of the surface of FIG. 7 is a graph showing a roughness curve measured in a direction perpendicular to a rolling direction of 7.
  • specimen No. 10 is an SEM image of the surface of No. 10; It is a graph which shows the roughness curve measured to the orthogonal
  • the gist of the present invention is to produce a titanium plate that exhibits both excellent seizure resistance and crack resistance and exhibits excellent formability by paying attention to the form of roughness and hardness of the surface of the titanium plate. is there.
  • the formability in the present invention means a general term for the workability of the plate material, the lubricity with the press tool, and the seizure resistance to the tool.
  • the titanium plate according to the present invention has an arithmetic average roughness (Ra) in the range of 0.15 to 1.5 ⁇ m, a maximum height (Rz) in the range of 1.5 to 9.0 ⁇ m, and a strain ( Rsk) is in the range of -3.0 to -0.5. Furthermore, the titanium plate according to the present invention has a Vickers hardness at a measurement load of 0.098 N on the surface higher than a Vickers hardness at a measurement load of 4.9 N, and the difference is 45 or less.
  • the arithmetic average roughness (Ra), the maximum height (Rz), and the degree of distortion (Rsk) conform to JISJB 0601: 2001.
  • the titanium plate according to the present invention basically has no hardened layer on the surface, and the surface was subjected to X-ray diffraction by a thin film method with an incident angle of 1 ° with an X-ray source of Cu—K ⁇ . At this time, the peaks of TiC and TiN are hardly detected.
  • the hardened layer means a film intentionally formed by heat treatment under controlled atmosphere conditions, and examples thereof include an oxide film, a nitride film, a carbide film, and a film containing one or more of these.
  • an oxide film formed by pickling treatment or a natural oxide film (passive film) naturally formed by being left in the atmosphere at room temperature is not a cured layer.
  • the thickness of a hardened layer is prescribed
  • recesses having a diameter of 10 ⁇ m or more are formed discontinuously on the surface.
  • the recess works as an oil reservoir and improves oil retention.
  • the concave portions are formed discontinuously, even if seizure occurs in a certain convex portion or a smooth portion, seizure stops in the concave portion, so that it is possible to prevent development of large seizure. .
  • the depth of the recess is smaller than the diameter of the recess, the recess can be prevented from acting as a notch (notch effect).
  • the arithmetic average roughness (Ra) generally used as a management index may not be sufficient. Since it has been elucidated, the maximum height (Rz) that defines the depth of the recess and the degree of distortion (Rsk) that defines the distribution state of the recess are defined as a management index in a specific numerical range.
  • the size of the recess can be determined by observing the surface of the titanium plate with an SEM (scanning electron microscope).
  • the titanium plate which concerns on this invention is not limited to the titanium plate of a specific composition, it is preferable that it is the following composition ranges from a viewpoint of ensuring the moldability of a base material. That is, in the titanium plate according to the present invention, the O content is suppressed to 1500 ppm or less, more preferably 1000 ppm or less, the Fe content is suppressed to 1500 ppm or less, more preferably 1000 ppm or less, and the H content is suppressed to 130 ppm or less.
  • the C content is suppressed to 800 ppm or less, the N content is suppressed to 300 ppm, and the other balance is Ti.
  • These O, Fe, N, C, and H are general impurity elements (elements that are not positively added) contained in pure titanium, that is, inevitable impurities.
  • the arithmetic average roughness (Ra) is defined to affect the average friction coefficient of the plate surface, but the depth of the recess cannot be expressed only by the arithmetic average roughness (Ra).
  • Rz is also defined.
  • the arithmetic average roughness (Ra) and the maximum height (Rz) are quantified information only in the height direction (longitudinal direction) of the roughness, and information on the shape in the horizontal direction (in-plane) is obtained. Not included. Therefore, the degree of distortion (Rsk) is defined in order to quantify the in-plane shape and distribution state of the recesses on the surface.
  • the arithmetic average roughness (Ra) is defined in order to affect the average friction coefficient of the plate material surface. If the arithmetic average roughness (Ra) is less than 0.15 ⁇ m, the oil retaining property cannot be exhibited. On the other hand, if the arithmetic average roughness (Ra) exceeds 1.5 ⁇ m, there is a possibility that the cracking due to the notch effect is induced and the formability is deteriorated, and the flow of the plate material is inhibited by the increase of the friction coefficient. Since local deformation is likely to occur, cracks are likely to occur, and the press load further increases.
  • the arithmetic average roughness (Ra) needs to be in the range of 0.15 to 1.5 ⁇ m.
  • the arithmetic average roughness (Ra) is preferably in the range of 0.2 to 1.5 ⁇ m, and more preferably in the range of 0.2 to 1.0 ⁇ m.
  • the maximum height (Rz) defines the depth of the recess. If the maximum height (Rz) is less than 1.5 ⁇ m, the depth of the recesses is insufficient and good oil retention cannot be exhibited, and seizure is likely to occur during molding. On the other hand, if the maximum height (Rz) exceeds 9.0 ⁇ m, it can be the starting point of cracking due to the notch effect. Therefore, the maximum height (Rz) needs to be in the range of 1.5 to 9.0 ⁇ m.
  • the maximum height (Rz) is preferably in the range of 1.8 to 9.0 ⁇ m, and more preferably in the range of 1.8 to 6.0 ⁇ m.
  • the degree of distortion (Rsk) corresponds to the distribution state / area ratio of the recesses. If the degree of strain (Rsk) is less than ⁇ 3.0, the area of the smooth portion decreases and the surface pressure on the smooth portion increases, so that local plastic deformation and seizure are likely to occur. On the other hand, when the degree of distortion (Rsk) exceeds ⁇ 0.5, even if the arithmetic average roughness (Ra) and the maximum height (Rz) are within a specified range, the convex portion or the surface has more corners. There are many cases.
  • the degree of strain (Rsk) needs to be in the range of -3.0 to -0.5, and preferably in the range of -3.0 to -1.0.
  • the degree of distortion (Rsk) is a target parameter for the center line of the amplitude distribution curve, and is calculated by the following equation (1).
  • the degree of distortion (Rsk) is 0 when the probability density function obtained from the roughness curve is a normal distribution (the vertical direction is the target), and is a negative ( ⁇ ) value when the concave portions are distributed on the smooth surface. A positive (+) value is obtained when convex portions are distributed on the surface.
  • the hardness of the outermost surface can be evaluated by the Vickers hardness at a measurement load of 0.098 N (10 g), and the hardness inside the material is evaluated by the Vickers hardness at a measurement load of 4.9 N (200 g). be able to. Moreover, the formation degree of a hardened layer can be evaluated by these differences. When a hardened layer of nitride or the like is formed on the surface, the difference between these Vickers hardnesses exceeds 45, and surface cracks are likely to occur during molding, resulting in deterioration of moldability. Therefore, the difference between these Vickers hardnesses needs to be 45 or less.
  • the difference in Vickers hardness is preferably 36 or less, and more preferably 35 or less.
  • the Vickers hardness tends to be higher as the load is lower even for a homogeneous material.
  • a specimen according to an example of the present invention described later when measured on a plate material in which a surface portion having a sufficient thickness (one side of 50 ⁇ m) is chemically removed, Vickers hardness at a measurement load of 0.098 N is obtained.
  • the measured value of was an average 12 higher than the measured value of Vickers hardness at a measurement load of 4.9 N.
  • the titanium plate according to the present invention preferably has a crystal grain size in the range of 20 to 80 ⁇ m in average section length when a cross section cut by a cutting method specified in JIS G 0552 is observed with an optical microscope. Since the irregularities on the surface are formed by reflecting the size of the crystal grain size in the pickling process, the irregularities on the surface of the titanium plate are moderately roughened by defining the range of the crystal grain size in this way, and thus excellent preservation is achieved. Oiliness can be obtained.
  • the average section length is less than 20 ⁇ m, the unevenness of the surface after the pickling step becomes shallow, The desired roughness cannot be obtained.
  • the crystal grain size when the cross section cut by the cutting method prescribed in JIS G 0552 is observed with an optical microscope exceeds 80 ⁇ m in average slice length, it is formed on the surface even if the pickling process is performed. Since the unevenness is shallow and the interval between the recesses becomes too wide, the desired roughness cannot be obtained. Therefore, excellent oil retention is not obtained and seizure is likely to occur, and once seizure occurs, it becomes difficult to be interrupted.
  • the average section length of the crystal grain size in the case of observing with a light microscope the section cut by the method defined in JIS G 0552 needs to be in the range of 20 to 80 ⁇ m.
  • the average section length of the crystal grain size is preferably in the range of 20 to 65 ⁇ m, and more preferably in the range of 35 to 65 ⁇ m. Is more preferable.
  • the thickness of the titanium plate according to the present invention can be appropriately determined according to handleability and usage, and is not particularly limited.
  • the thickness of the titanium plate is preferably 1.0 mm or less.
  • the use of the titanium plate according to the present invention is not limited to the above-mentioned members for heat exchangers.
  • consumer products such as camera bodies and kitchen equipment, transport equipment members such as motorcycles and automobiles, and home appliances. It can also be used for exterior materials such as.
  • the titanium plate according to the present invention has been described in detail above. According to such a titanium plate, the surface roughness is appropriately controlled by the arithmetic average roughness (Ra), the maximum height (Rz), and the degree of distortion (Rsk), so that excellent oil retention can be obtained. . Therefore, as a result of maximizing the lubrication effect of the press oil during press molding, it becomes possible to obtain good seizure resistance. In addition, by appropriately controlling the surface roughness in this way, it is possible to prevent the notch effect and to prevent the occurrence of surface cracks. Furthermore, since no hardened layer is formed on the surface of the titanium plate, it is possible to make it difficult for surface cracks to occur during molding. Therefore, the titanium plate according to the present invention can exhibit excellent press formability. In addition, since the titanium plate according to the present invention has good seizure resistance, it is difficult for titanium to adhere to the molding die, and it is possible to reduce the frequency of polishing the molding die, thereby improving productivity. Can do.
  • Ra arithmetic average
  • the titanium plate demonstrated above can be suitably manufactured with the manufacturing method of the titanium plate which concerns on this invention demonstrated below.
  • two typical production steps for a titanium plate after cold rolling are introduced. First, vacuum annealing is performed after cold rolling, and second, atmospheric annealing is performed after cold rolling, followed by pickling.
  • a hardened layer is easily formed on the surface of the titanium plate during cold rolling and subsequent vacuum annealing. Even when the vacuum annealing atmosphere is an inert atmosphere and the oxygen and nitrogen partial pressures are reduced, titanium carbide is formed on the surface when the lubricating oil during cold rolling remains on the titanium plate surface. A hardened layer is formed. For this reason, there is a possibility that a titanium plate that is easily cracked at the time of press forming is produced.
  • the latter production process is suitable for producing a titanium plate excellent in press formability because the surface hardened layer is removed from the pickled titanium plate.
  • the seizure resistance with the molding die is insufficient, and seizure may occur easily.
  • surface irregularities are formed so as to improve the oil retention of the lubricating oil, and the crystal grain size and pickling conditions are set to specific conditions in order to control the form. .
  • skin pass rolling under specific conditions is performed after pickling. Thereby, seizure resistance can be improved without using a hardened layer.
  • the manufacturing method of the titanium plate which concerns on this invention is demonstrated concretely.
  • the method for manufacturing a titanium plate according to the present invention includes an atmospheric annealing step S1, a pickling step S2, and a skin pass rolling step S3, and each step is performed in this order.
  • the process up to the cold rolling does not greatly affect the surface form of the titanium plate according to the present invention, the casting process, the soaking process, the hot rough rolling process, What is necessary is just to perform a finishing process, a winding process, a cold rolling process, etc. Below, each process of the manufacturing method of the titanium plate of this invention is demonstrated.
  • the atmospheric annealing step S1 is a step of performing atmospheric annealing on the titanium plate after cold rolling so that the crystal grain size becomes 20 to 80 ⁇ m.
  • the crystal grain size is set to 20 to 80 ⁇ m in the atmospheric annealing step S1
  • irregularities can be formed on the surface in an appropriate size (depth) and distribution state by a subsequent pickling step S2.
  • the depth of the recesses on the surface is related to the maximum height (Rz), and the distribution state of the recesses is related to the degree of strain (Rsk).
  • continuous annealing (processing time is about 30 seconds to about 5 minutes) is performed.
  • General atmospheric annealing is performed at 700 to 800 ° C., but in the present invention, in order to keep the crystal grain size within a desired range, it is preferable from the viewpoint of productivity that the temperature is 750 to 850 ° C.
  • the crystal grain size depends on the annealing temperature and annealing time. If the temperature is higher than the recrystallization temperature (600 ° C. or higher), it is possible to obtain a desired crystal grain size by performing long-term atmospheric annealing even in a temperature range of less than 750 ° C.
  • the crystal grain size can be increased as the annealing temperature is increased if the annealing time is constant.
  • the annealing temperature exceeds 850 ° C., the ⁇ phase precipitates during the annealing, so that the crystal grains become fine after cooling, and if it is processed for several minutes, it may be 20 ⁇ m or less. Therefore, the annealing temperature in the atmospheric annealing step S1 needs to be 850 ° C. or lower.
  • the pickling step S2 is a step of pickling the titanium plate after the atmospheric annealing step S1 in a pickling bath having a nitric acid / hydrofluoric acid ratio of 1 or more and 10 or less.
  • a pickling bath within the composition range described above it is possible to remove about 20 ⁇ m on one side by a treatment for about 60 seconds at a liquid temperature of 65 ° C.
  • irregularities can be formed in a desired form on the surface of the titanium plate, and the hardened layer formed on the surface can be removed. If it does in this way, the Vickers hardness in the measurement load 0.098N in the surface is higher than the Vickers hardness in the measurement load 4.9N, and the difference can be 45 or less.
  • the nitric acid / hydrofluoric acid ratio is less than 1, the unevenness of the surface of the titanium plate becomes too fine, and a lot of small and shallow irregularities are formed, so that the oil retaining effect cannot be obtained.
  • the nitric acid / hydrofluoric acid ratio exceeds 10, the pickling speed becomes slow and it becomes difficult to remove the scale and the pickling is performed smoothly, so that the unevenness formed after pickling is small or formed. Therefore, excellent oil retention cannot be obtained.
  • the pickling temperature is not particularly limited. Since the pickling speed changes by changing the temperature, the bath temperature may be set in the range from room temperature to 70 ° C., and the temperature may be set according to the pickling time determined from the configuration of the production line.
  • the removal amount of the surface of the titanium plate by the pickling step S2 is preferably 1 ⁇ m or more on one side.
  • the upper limit of the removal amount is not particularly limited, but is preferably 20 ⁇ m or less on one side from the viewpoint of productivity and yield.
  • the skin pass rolling step S3 is a step of performing skin pass rolling on the titanium plate after the pickling step S2 at a rolling reduction of 0.2 to 1.0%.
  • the skin pass rolling step S3 can be performed at room temperature, whereby the convex portions formed on the surface can be leveled to form a titanium plate having appropriate smooth portions and concave portions.
  • the local surface pressure can be lowered and the effect of reducing the friction coefficient can be obtained.
  • the arithmetic average roughness (Ra) indicating the average friction coefficient on the surface of the titanium plate can be set in the range of 0.15 to 1.5 ⁇ m, and the depth of the recess is indicated.
  • the maximum height (Rz) can be in the range of 1.5 to 9.0 ⁇ m
  • the degree of distortion (Rsk) indicating the distribution state of the recesses can be in the range of ⁇ 3.0 to ⁇ 0.5. .
  • the rolling reduction in the skin pass rolling step S3 needs to be 0.2 to 1.0%.
  • the rolling reduction in the skin pass rolling step S3 is preferably 0.3 to 0.8%.
  • the above-described titanium plate of the present invention can be preferably manufactured.
  • the effect of the present invention was verified using a titanium material equivalent to JIS-1 type.
  • the effect of the present invention is also effective for titanium plates using other grades of pure titanium materials and titanium alloy materials, including JIS-2 equivalent titanium materials.
  • cold rolled sheets of industrial pure titanium JIS-1 type
  • the chemical composition of this cold-rolled sheet is O: 450 ppm, Fe: 250 ppm, N: 40 ppm, and the balance is Ti and inevitable impurities.
  • a cold-rolled sheet that had been cold-rolled under normal conditions was air-annealed at a temperature of 750 to 850 ° C.
  • the crystal grain size is controlled by the annealing conditions of this atmospheric annealing.
  • the annealing conditions are shown in Table 1.
  • the titanium plate was immersed in a hydrofluoric acid nitric acid mixture having the concentrations shown in Table 1 and heated to 60 ° C., and pickled with a removal amount of 10 ⁇ m on one side, thereby forming a test piece 1 having irregularities formed on the surface. ⁇ 18 are obtained. Since the pickling speed varies depending on the nitric acid / hydrofluoric acid ratio, the pickling speed in the solution of each blending ratio was obtained by preliminary experiments, and the pickling time was set so as to obtain a predetermined removal amount.
  • test body 19 a test body (test body 19) that was subjected to vacuum annealing after cold rolling was prepared.
  • the test body 19 is as above-mentioned to a cold rolling process, it is obtained by performing vacuum annealing after degreasing
  • vacuum annealing the pressure in the chamber is once reduced to 1.3 ⁇ 10 ⁇ 3 Pa, the furnace is heated to 650 ° C., and oxygen gas is introduced until 6.7 ⁇ 10 ⁇ 3 Pa is reached. Cooling was performed after holding for a time.
  • the crystal grain size was measured by cutting each test specimen by a cutting method specified in JIS G 0552 and measuring the crystal grain size of the cross-sectional structure observed with an optical microscope.
  • the crystal grains had an equiaxed shape.
  • the measurement of Vickers hardness was carried out by a method based on JIS Z 2244 with the measurement surface as the surface of the test specimen.
  • the measurement load was 4.9 N (200 g) and 0.098 N (10 g), 10 points were measured for each measurement load, and the average value was used as the measurement value.
  • a micro Vickers hardness tester (MATSUZAWA SEIKI DMH-1) is used for measurement with a measurement load of 4.9N, and an ultra micro Vickers hardness tester (AKASHI MVK-G3) is used for measurement with a measurement load of 0.098N. It was.
  • Table 1 shows the measurement value of the measurement load of 4.9N and the difference between the measurement load of 0.098N and the measurement load of 4.9N.
  • the surface roughness was measured using a surface roughness shape measuring machine (Surfcom 1400D manufactured by Tokyo Seimitsu Co., Ltd.) according to a method based on JIS B 0601: 2001. At this time, the measurement distance was 7 mm, the measurement speed was 0.3 mm / sec, 5 points each in parallel and perpendicular to the rolling direction were measured, and the average value was defined as the surface roughness.
  • Evaluation of formability was performed by performing press molding using a molding die simulating the heat exchange part of the plate heat exchanger for each specimen.
  • press molding was performed by an 80 ton hydraulic press.
  • press oil having a kinematic viscosity of 34 mm 2 / s (40 ° C.) is applied to both surfaces of each test body, and each test is performed so that the rolling direction of each test body coincides with the vertical direction in FIG.
  • the press was performed at a speed of 1 mm / s and an indentation depth of 3.8 mm. And formability was evaluated by the number of cracks observed in each specimen after press molding. A specific evaluation method will be described below.
  • the presence or absence of cracks in the test specimen was visually observed at 36 intersection points between the ridge line portion shown in FIG. 2A and the dotted lines of the measurement positions A, B, C, C ′, D, and E.
  • the measurement position C ′ is a valley portion located between adjacent ridge line portions as shown in FIG.
  • For the measurement positions A, C, C ′, and E, which are the starting points of cracking two points were given when no cracking or constriction was observed, one point was given for constriction, and 0 point was given for cracking. .
  • For the measurement positions B and D 1 point was given when no cracking or constriction was observed, 0.5 points were given when constriction was found, and 0 points were given when cracking was found.
  • Formability score F ⁇ G ⁇ ⁇ E (ij) / R (j) / ( ⁇ A , C , C ′ , E 2 / R (j) + ⁇ B , D 1 / R (j)) ⁇ 100 ⁇ ⁇ Formula (2)
  • A, C, C ′, E, E (ij) 1.0 ⁇ (no crack; 2, constriction; 1, crack; 0)
  • the temperature (T), the lubricating oil viscosity ( ⁇ ), the test piece plate thickness (t), the angle ( ⁇ ) of the twill lines of the mold, and the pitch (p) were constant, so that F ⁇ G
  • the score was calculated as 1.
  • Table 1 shows the moldability score of each specimen. A specimen having a moldability score of 70 or more was determined to have good moldability, and a specimen having a moldability score of less than 70 was determined to have poor moldability.
  • test bodies 8 to 11 and 15 to 17 had low surface hardness (Vickers hardness), they did not show excellent moldability (Comparative Example). This is because the surface roughness of the specimen was not formed in a good form, and the oil retention was deteriorated by either the unevenness becoming shallow or the interval between the recesses becoming wide. It is thought to be the cause.
  • the specimen 14 has a crystal grain size that satisfies the requirements of the present invention, but has poor moldability (comparative example). This is because the reduction ratio of the skin pass rolling performed after the pickling process was too high, and the good unevenness formed on the surface of the test body 14 in the pickling process was broken to become a smooth surface, and the oil retention was deteriorated. Conceivable. In addition, since the amount of plastic deformation applied before forming is large, the amount of plastic deformation in press forming is reduced, so it is considered that excellent formability could not be obtained.
  • FIG. 3 shows an SEM image and a roughness curve of the surface of the test body 7
  • FIG. 4 shows an SEM image and a roughness curve of the surface of the test body 10.
  • the surface of the test body 7 is formed by dispersing a plurality of concave portions in a smooth portion.
  • these recesses act as oil reservoirs, so that the oil retention is excellent, and good seizure resistance and crack resistance can be obtained despite the pickled surface. It is considered that excellent results were obtained.
  • FIG. 3 (b) in the width of 3 mm at an arbitrary position on the surface of the test body 7, the concave portions are formed to be distributed with an appropriate distribution state, and the convex portions are almost formed. Not.

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Abstract

L'invention porte sur une plaque en titane qui résiste bien à la brûlure et à la fissuration et qui présente une excellente formabilité à la presse. Ladite plaque en titane est caractérisée par une rugosité moyenne arithmétique (Ra) dans la plage de 0,15 à 1,5 µm, une hauteur maximale (Rz) dans la plage de 1,5 à 9,0 µm, et une asymétrie (Rsk) dans la plage de -3,0 à -0,5. La plaque en titane est en outre caractérisée en ce que la dureté de surface Vickers à une charge de mesure de 0,098 N est supérieure à la dureté de surface Vickers à une charge de mesure de 4,9 N, et que la différence n'est pas supérieure à 45.
PCT/JP2010/057482 2009-04-28 2010-04-27 Plaque en titane et procédé de fabrication de plaques en titane Ceased WO2010126051A1 (fr)

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JP2013011013A (ja) * 2011-05-30 2013-01-17 Kobe Steel Ltd プレス成形性と強度のバランス、及び耐食性に優れた純チタン板、並びにその製造方法
CN103846277A (zh) * 2014-03-02 2014-06-11 首钢总公司 一种提高海底管线钢低温止裂韧性的生产方法
CN104226721A (zh) * 2014-09-05 2014-12-24 常熟市佳泰金属材料有限公司 一种新型纯钛卷的生产设备
JP6119927B1 (ja) * 2016-07-08 2017-04-26 新日鐵住金株式会社 チタン板及びその製造方法

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JP5654933B2 (ja) * 2011-04-01 2015-01-14 株式会社神戸製鋼所 高耐力でプレス成形性に優れたチタン板
WO2012144561A1 (fr) * 2011-04-22 2012-10-26 新日本製鐵株式会社 Brame de titane destinée au laminage à chaud et procédé de fabrication de celle-ci
CN103433320B (zh) * 2013-08-13 2016-03-02 洛阳双瑞精铸钛业有限公司 一种由纯钛板坯制备钛阳极板的加工方法
TWI534278B (zh) * 2013-12-26 2016-05-21 China Steel Corp Method for making titanium sheet
CN105750853A (zh) * 2014-12-15 2016-07-13 无锡市普尔换热器制造有限公司 钛合金板翅式换热器的清洗工艺
JP6536076B2 (ja) * 2015-02-24 2019-07-03 日本製鉄株式会社 チタン板とその製造方法
JP6172408B1 (ja) 2016-01-18 2017-08-02 新日鐵住金株式会社 チタン板
US20190226073A1 (en) * 2016-06-30 2019-07-25 Nippon Steel & Sumitomo Metal Corporation Titanium sheet and method for producing the same
CN109751487A (zh) * 2017-11-07 2019-05-14 丹阳市日晟工业设备有限公司 一种波浪形板状冲压件
JP6897561B2 (ja) * 2017-12-28 2021-06-30 日本製鉄株式会社 チタン材および機器
CN111054751B (zh) * 2019-12-30 2021-05-28 西南铝业（集团）有限责任公司 一种粗糙度u型分布的铝合金毛化板及其制备方法
JP7525784B2 (ja) * 2020-09-16 2024-07-31 日本製鉄株式会社 チタン材およびチタン材の製造方法

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JP2003236604A (ja) * 2002-02-19 2003-08-26 Sumitomo Metal Ind Ltd チタン材の製造方法と潤滑剤
JP2004244671A (ja) * 2003-02-13 2004-09-02 Nippon Steel Corp 成形性と潤滑性に優れたチタン板とその製造方法
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JP2013011013A (ja) * 2011-05-30 2013-01-17 Kobe Steel Ltd プレス成形性と強度のバランス、及び耐食性に優れた純チタン板、並びにその製造方法
CN103846277A (zh) * 2014-03-02 2014-06-11 首钢总公司 一种提高海底管线钢低温止裂韧性的生产方法
CN104226721A (zh) * 2014-09-05 2014-12-24 常熟市佳泰金属材料有限公司 一种新型纯钛卷的生产设备
JP6119927B1 (ja) * 2016-07-08 2017-04-26 新日鐵住金株式会社 チタン板及びその製造方法
WO2018008151A1 (fr) * 2016-07-08 2018-01-11 新日鐵住金株式会社 Feuille de titane et son procédé de production
US10900109B2 (en) 2016-07-08 2021-01-26 Nippon Steel Corporation Titanium sheet and method for manufacturing the same

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