WO2019193655A1 - チタン板 - Google Patents
チタン板 Download PDFInfo
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- WO2019193655A1 WO2019193655A1 PCT/JP2018/014313 JP2018014313W WO2019193655A1 WO 2019193655 A1 WO2019193655 A1 WO 2019193655A1 JP 2018014313 W JP2018014313 W JP 2018014313W WO 2019193655 A1 WO2019193655 A1 WO 2019193655A1
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- titanium
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- titanium plate
- rolling
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- 239000010936 titanium Substances 0.000 title claims abstract description 126
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 119
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 118
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 48
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 239000002344 surface layer Substances 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 230000001133 acceleration Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000004453 electron probe microanalysis Methods 0.000 claims 1
- 150000003608 titanium Chemical class 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 description 46
- 238000000137 annealing Methods 0.000 description 43
- 238000005097 cold rolling Methods 0.000 description 38
- 238000000034 method Methods 0.000 description 32
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 17
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- 238000012937 correction Methods 0.000 description 11
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- 239000002585 base Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
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- 229910004298 SiO 2 Inorganic materials 0.000 description 7
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
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- 238000007373 indentation Methods 0.000 description 5
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- 229910052759 nickel Inorganic materials 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000005260 corrosion Methods 0.000 description 4
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- 238000004519 manufacturing process Methods 0.000 description 4
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- 239000010409 thin film Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
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- 229910000831 Steel Inorganic materials 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
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- 229910002703 Al K Inorganic materials 0.000 description 1
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- 239000002390 adhesive tape Substances 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
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Images
Classifications
-
- 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
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
Definitions
- the present invention relates to a titanium plate.
- Titanium plates are metal materials with excellent corrosion resistance, and are used in heat exchangers using seawater, various chemical plants, and the like. Titanium plates are also used as structural members because of their high specific strength.
- the titanium plate may be subjected to a surface treatment in order to impart various characteristics.
- the titanium plate since titanium cannot exhibit sufficient corrosion resistance in an alkaline environment, the titanium plate can be used even in an alkaline environment by plating a resin having alkaline corrosion resistance or a metal such as Ni.
- a titanium plate can be used as a speaker diaphragm whose sound quality is controlled by plating a metal such as Al having different rigidity, a ceramic such as AlN, or a resin.
- various properties such as thermal conductivity and wear resistance can be imparted to the titanium plate, and highly functional products can be manufactured.
- Patent Document 1 discloses an invention that improves the adhesion between the outermost coating layer and a base material (including a pre-plated layer) by performing hot-dip aluminum plating on titanium in advance.
- Patent Document 2 discloses an invention for improving the adhesion between a noble metal plating layer and a material to be plated by cleaning C or N on the surface of the material to be plated for noble metal plating.
- Patent Document 3 discloses an invention in which graphite is physically coated on the surface of a base material by pressure-bonding the graphite to the base material.
- Patent Document 4 discloses an invention in which titanium carbonitride is formed on the surface by cold working and annealing to improve corrosion resistance.
- Non-Patent Document 1 describes stress and friction generated between rolling rolls, lubricating oil, and material to be rolled in the rolling process. An analysis method for force is disclosed.
- Patent Document 5 discloses a technique for forming a rolled deteriorated layer containing titanium carbide (TiCx) by rolling and improving the adhesion with a carbon film to be formed thereafter by the anchor effect.
- Patent Documents 1 to 5 with the inventions disclosed in Patent Documents 1 to 5 and the method disclosed in Non-Patent Document 1, titanium excellent in adhesion between the surface coating layer and the base material and workability while suppressing an increase in processing cost.
- the board cannot be reliably provided.
- An object of the present invention is to provide a titanium plate excellent in adhesion to the surface coating layer and workability.
- TiCx titanium carbide
- Patent Document 5 The titanium carbide (TiCx) disclosed in Patent Document 5 can be used to form irregularities on the surface of the titanium plate and improve the adhesion of the film by the anchor effect, but the anchor effect is insufficient. It was. In addition, since no consideration is given to the workability of the titanium plate, there remains a problem that the workability is deteriorated by the titanium carbide.
- Cr + Ni + Mo + V + Nb may be 0.00% to 1.00% by mass.
- Sn + Co + Zr + Mn + Ta + W + Hf + Pd + Ru may be 0.00 to 1.00% by mass%.
- the carbon content measured using XPS may be 10.0 at% or more.
- the ratio of the characteristic X-ray (K ⁇ -ray) intensity from the surface obtained by EPMA at an acceleration voltage of 10 kV and the K ⁇ -ray intensity in graphite may be 1.00% or more.
- Chemical composition of titanium plate according to the present invention is, in mass%, Fe: 0.20% or less, O: 0.12% or less, N: 0.08% or less, C: 0.10% or less, H: 0.013% or less, the balance Ti and impurities. “%” Relating to the chemical composition described below means “% by mass” unless otherwise specified.
- the titanium plate according to the present invention includes, for example, first to fourth types defined by JIS H4600 (2012) and Grades 1 to 4 defined by ASTM B265 corresponding thereto, and 3,7025 standardized by DIN 17850. 3, 7035, 3 ⁇ 7055 (also referred to as industrial pure titanium).
- (1-1) Fe 0.00 to 0.20%
- the Fe content is 0.20% or less, desirably 0.15%, and more desirably 0.10% or less.
- the lower limit of the Fe content is 0.00%.
- the lower limit of the Fe content may be 0.01%, 0.02%, or 0.03%.
- (1-2) O 0.00 to 0.12% O increases the strength of the titanium plate, but greatly reduces workability. Therefore, the O content is 0.12% or less, desirably 0.10% or less, and more desirably 0.08% or less. On the other hand, the lower limit of the O content is 0.00%. However, since the O content is unavoidable industrially, the lower limit of the O content may be 0.01%, 0.02%, or 0.03%.
- N 0.00 to 0.08% N, like O, reduces the workability of the titanium plate. Therefore, the N content is 0.08% or less, desirably 0.05 or less, and more desirably 0.03 or less. On the other hand, the lower limit of the N content is 0.00%. However, since the N content is unavoidable industrially, the lower limit of the N content may be 0.01%, 0.02%, or 0.03%.
- (1-4) C 0.00 to 0.10% C has less influence on strength and workability than O and N.
- the upper limit of the C content is 0.10%, desirably 0.08 or less, and more desirably 0.03 or less.
- the lower limit of the C content is 0.00%.
- the lower limit of the C content may be 0.01%, 0.02%, or 0.03%.
- H 0.000 to 0.013%
- H is an element that causes embrittlement. Since the solid solubility limit at room temperature is around 10 ppm, there is a concern that hydride is formed and embrittlement occurs when more H is contained. Generally, when the content is 0.013% or less, there is a concern about embrittlement, but it is used without any problem in practice. Preferably it is 0.010% or less, More preferably, it is 0.008% or less, 0.006% or less, 0.004% or less, or 0.003% or less.
- the lower limit of the H content is 0.000%. If necessary, the lower limit may be 0.001%, 0.002%, or 0.003%.
- metal elements derived from scrap When the use of scrap as a raw material is promoted, metal elements other than these elements are mixed in addition to the above-described elements (Fe, O, N, C, H). Although strict management can prevent the mixing of these elements, the processing cost increases. In the present invention, in order to provide an inexpensive titanium plate, mixing of metal elements derived from scrap is allowed as much as possible within a range not impairing the effects of the present invention. Examples of metal elements derived from scrap include Al, Cu, Cr, Ni, Mo, V, Sn, Co, Zr, Nb, Si, Mn, Ta, W, Hf, Pd, and Ru.
- Al 0.00 to 0.50% Al does not promote the formation of the ⁇ phase, but reduces workability. For this reason, the Al content is 0.50% or less, desirably 0.40% or less, and more desirably 0.30% or less.
- Cu 0.00 to 0.50% Cu does not decrease workability as much as Al. Therefore, the Cu content is 0.50% or less, desirably 0.40% or less, and more desirably 0.30% or less.
- Si 0.00 to 0.30% Since Si has a greater influence on workability than Al, the Si content is 0.30% or less, desirably 0.20% or less, and more desirably 0.15% or less.
- the contents of Sn, Co, Zr, Mn, Ta, W, Hf, Pd, and Ru are 0.50% or less, respectively, and the total content is 1.00% or less, preferably It is 0.80% or less, more preferably 0.60% or less.
- the bulk component (chemical composition) of the titanium plate is an analysis value analyzed as follows. That is, a sample for component analysis is taken from a product plate, Fe and other contained metals are analysis values by inductively coupled plasma (ICP) emission analysis method, O is an analysis value by inert gas melting infrared absorption method, N is an analysis value by an inert gas melting thermal conductivity method, and C is an analysis value by a high frequency combustion infrared absorption method.
- ICP inductively coupled plasma
- O is an analysis value by inert gas melting infrared absorption method
- N is an analysis value by an inert gas melting thermal conductivity method
- C is an analysis value by a high frequency combustion infrared absorption method.
- the analysis of C in order to exclude the influence of C adhering to the vicinity of the surface, it is necessary to analyze the range of 1/4 to 3/4 of the plate thickness from the surface. However, when analyzing other elements, there is no problem using the full thickness.
- Arithmetic mean roughness Ra of the titanium plate surface according to the present invention As will be described later, even if the number density and width of the irregularities on the surface of the titanium plate are controlled, when the depth is deep (when the height difference is large), it becomes the starting point of stress concentration and leads to fracture. It also becomes difficult to obtain a smooth surface when performing a surface treatment on the titanium plate. For this reason, it is effective to keep the surface roughness of the titanium plate small. From such a viewpoint, the arithmetic average roughness Ra of the surface of the titanium plate according to the present invention is 0.40 ⁇ m or less, and more desirably 0.30 ⁇ m or less. The lower limit is 0.05 ⁇ m or more so that the anchor effect can be sufficiently obtained.
- the arithmetic average roughness Ra is a value defined in JIS B 0601: 2001, and is obtained from a cross-sectional curve of the actual surface measured in a direction perpendicular to the rolling direction on the rolled surface of the titanium plate.
- the arithmetic average roughness Ra was calculated
- the evaluation length (reference length) at this time is about 300 ⁇ m (exactly 298 ⁇ m).
- the average value of the measured values at five locations (field of view) was used.
- FIG. 1 is an explanatory diagram showing an example of a roughness curve on the surface of a titanium plate according to the present invention.
- the unevenness (valley and peak) present on the surface of the titanium plate according to the present invention is a fine crack.
- the number density and average interval (also referred to as uneven width) of the fine concave portions (valley portions) and convex portions (peak portions) are important for improving uniform film adhesion.
- Titanium carbide (TiCx) exists in the convex part and the concave part.
- a convex part is formed when the hardened layer of the surface layer of the titanium plate was cracked by cold rolling or dull roll under strong pressure.
- the height from a reference line which is a straight line drawn so that the sum of squares of deviation from the roughness curve determined as a cutoff value of 0.08 mm is minimized.
- a peak of 0.1 ⁇ m or more is defined as a convex part (also referred to as a peak part).
- a valley having a depth of 0.1 ⁇ m or more from the reference line (average line) is defined as a recess (also referred to as a valley).
- the number density of convex portions and concave portions is defined as the number of convex portions and concave portions (peaks and valleys) existing in the length of 1 mm of the roughness curve.
- the average interval between recesses is defined as the average value of the widths of protrusions and recesses (peaks and valleys). This is because the film formed on the surface of the titanium plate enters the recesses and has an effect of improving the adhesion by the anchor effect, so that the peak part is less than 0.1 ⁇ m in height and the valley part is less than 0.1 ⁇ m in depth. This is because the anchor effect is small. Taking FIG.
- the uneven width is the average value of the lengths of the reference lines cut by the peaks 1, 2, and 4 (W1, W2, and W4 in FIG. 1) and the length of the reference lines cut by the valley 3 (W3 in FIG. 1). (W1 + W2 + W3 + W4) / 4.
- FIG. 2 is a graph showing the relationship between adhesion and unevenness.
- the white circle plot “ ⁇ ” in FIG. 2 indicates that the adhesion is good and that the Erichsen value is 10 mm or more, and the black circle plot “ ⁇ ” indicates that the adhesion is inferior.
- the plot “x” indicates that the Eriksen value is less than 10 mm.
- the adhesiveness is excellent when the number density is 30 pieces / mm or more and the average interval (unevenness width) is 20 ⁇ m or less.
- the upper limit of the average interval (uneven width) may be 17 ⁇ m, 15 ⁇ m, or 13 ⁇ m. However, if the uneven width is too narrow, it is difficult for the coating to enter the recess when the coating is formed, and as a result, the anchor effect cannot be obtained.
- the lower limit of the average interval (unevenness width) is preferably 5 ⁇ m, but may be 8 ⁇ m, 10 ⁇ m, or 12 ⁇ m.
- the number density of convex portions and concave portions increases, the adhesion to the coating is improved, and the formability is improved by increasing the stress concentration starting point.
- the number density of the convex portions and the concave portions is 30 pieces / mm or more and 100 pieces / mm or less, preferably 30 pieces / mm or more and 90 pieces / mm or less, more preferably 30 pieces / mm or more and 80 pieces or less. / Mm or less.
- the upper limit of the number density of the convex portions and the concave portions may be 70 pieces / mm, 60 pieces / mm, or 50 pieces / mm. This is because when the number density is less than 30 pieces / mm, the coating formed on the surface of the titanium plate is difficult to enter the concave portion and it is difficult to obtain the anchor effect.
- Carbon content on the surface of the titanium plate according to the present invention In order to effectively form unevenness effective for the anchor effect, it is preferable that surface hardening with carbon is performed before forming the unevenness. For this reason, the surface of the titanium plate after the formation of the unevenness that has obtained the above-described number density and unevenness width of the unevenness contains more carbon than the central portion of the thickness. For example, it is preferable that 10 at% or more of carbon is contained on the average in a region having a depth of 0.1 ⁇ m to 1.0 ⁇ m from the surface of the titanium plate. The carbon in this region may be 12 atm% or more, 15 atm% or more, or 17 atm% or more on average.
- the carbon in this region may be 32 atm% or less, 30 atm% or less, or 28 atm% or less on average.
- the analysis of the carbon amount is performed by repeating element amount measurement by sputtering and XPS (X-ray photoelectron spectroscopy) a plurality of times. Since the depth position in XPS is managed by the distance at which SiO 2 is sputtered by Ar ions, the average carbon content is 10 atm% or more at a depth of 0.1 ⁇ m to 0.5 ⁇ m from the surface at this SiO 2 conversion distance. If it is.
- elements other than carbon require nitrogen, oxygen, and titanium, and the elements detected by qualitative analysis are measured in the same manner.
- Carbon on the surface layer of the titanium plate is supplied from the rolling oil, and is introduced only into the extreme surface layer of the titanium plate (for example, a depth of 1 ⁇ m or less from the surface) by cold rolling on the surface layer.
- the degree of hardening differs depending on the solid solution amount of solid solution strengthening and the work amount of work hardening. In work hardening, deformation concentrates on a soft part, so that the soft part preferentially hardens. However, since work hardening alone does not provide a sufficiently uniform effect, the soft part can be further reduced by work hardening by reducing the soft part with carbon or titanium carbide.
- the surface layer of the titanium plate is strengthened, and the surface layer is work-hardened by processing, and due to the synergistic effect with titanium carbide formed on the surface layer of the titanium plate Hardens almost uniformly.
- the surface layer When the surface layer is uniformly hardened, fine cracks are uniformly generated during cold rolling, and desired irregularities are uniformly formed on the surface. As described above, when the surface layer contains carbon, it is considered that uneven curing due to processing is alleviated. For this reason, it is desirable that the surface layer of the titanium plate after forming the irregularities is also high carbon.
- the carbon introduced into the surface layer during processing can be evaluated by EPMA (Electron Probe Micro Analyzer).
- EPMA Electro Probe Micro Analyzer
- the evaluation with EPMA has no problem even when it is cold-rolled or after annealing. This is because the EPMA evaluation range is about 1 to 2 ⁇ m on the surface layer, and the diffusion into the interior by annealing is generally within this range.
- the plate after annealing is ultrasonically cleaned with acetone and then measured.
- the evaluation of the carbon content is expressed as an intensity ratio when the intensity of the characteristic X-ray K ⁇ of the standard sample is 100%.
- graphite purity 99.9% or more and relative density of sintered body (sintered body density / ideal density) of 99% or more
- the measurement is performed at an acceleration voltage of 10 kV in an area of 40000 ⁇ m 2 or more.
- the graphite standard sample and the sample are measured by surface analysis.
- the beam diameter is set to 1 ⁇ m or less, and the intensity of each point is obtained at an irradiation time of 50 ms / point at a pitch of 2 ⁇ m, and the average intensity is used.
- the irradiation current is 5 nA when measuring a standard sample, 20 nA when measuring a sample, and the intensity of the standard sample is converted to the same level as the measurement at 20 nA by multiplying the obtained value by four times. .
- the obtained strength ratio is preferably 1.00% or more, more preferably 1.30% or more, 1.50% or more, or 2.00% or more.
- the amount is too large, carbon forms a large amount of titanium carbide when annealed, thereby reducing the formability after annealing.
- the intensity ratio is preferably 5.00% or less, and may be 4.70% or less, or 4.50% or less.
- X-rays were Cu-K ⁇ , and the diffraction step curve obtained by the ⁇ / 2 ⁇ method with a measurement step angle (2 ⁇ ) of 0.06 ° was smoothed (weighted average method at 9 points), background processing (Sonnevelt- Visser method), and the peak corresponding to K ⁇ 1 obtained after removing the peak due to K ⁇ 2 when the intensity ratio K ⁇ 2 / K ⁇ 1 between K ⁇ 1 and K ⁇ 2 is 0.497 is used.
- the titanium carbide peaks are the (111) (200) (220) planes, and the Ti peaks are all ⁇ -Ti peaks observed in the range of 2 ⁇ of 30 ° to 130 °.
- FIG. 3 shows an example of the X-ray diffraction pattern.
- titanium carbide peaks are P2, P5, and P7, and the integrated intensities of these peaks are I (111), I (200), and I (220), respectively.
- the determination of the peak not considered is whether or not the integrated intensity is 5% or less of Ic. Only the peak at the position described in FIG.
- the abundance (Ic / Im ⁇ 100) of titanium carbide on the surface of the titanium plate after forming the irregularities is 0.8% or more and 5.0% or less. This is because when titanium carbide exceeding 5.0% is detected, the surface layer of the titanium plate is too hard, and a problem arises in the formability of the titanium plate.
- a preferable upper limit of the abundance of titanium carbide (Ic / Im ⁇ 100) may be 4.0%, 3.5%, 3.0%, or 2.5%.
- the lower limit of the amount of titanium carbide (Ic / Im ⁇ 100) is 0.8%, and the lower limit may be 1.0%, 1.5%, or 2.0%.
- the surface hardness is preferably 200 or more and 300 or less in the Vickers hardness HV0.025 in consideration of the balance between the formability of the titanium plate and the improvement in adhesion with the coating layer of the titanium plate.
- the upper limit of Vickers hardness HV0.025 may be 270, 260, or 250.
- the lower limit of the Vickers hardness HV 0.025 may be 210, 220, or 230.
- the Vickers hardness was measured at a load of 25 gf, 10 points were randomly measured so that the indentations were separated by a distance of 5 or more indentation sizes on the plate surface, and the average value was evaluated.
- TiCx exists in the vicinity of the apex of the convex portion and does not exist in the concave portion as it is in cold rolling.
- the rolling oil that cannot be removed by washing remains in the recesses and forms TiCx by annealing.
- carbon diffuses inside during annealing the carbon distribution when unevenness is formed under large pressure and the carbon distribution after annealing are different. Since the unevenness effective for adhesion is 0.1 ⁇ m or more, the desired unevenness cannot be formed during cold rolling unless sufficient carbon is present in the region of 0.1 ⁇ m or more from the plate surface.
- the amount of carbon of 0.1 ⁇ m to 0.5 ⁇ m was evaluated from the surface after annealing, and when the value was 10 at% or more, the desired unevenness was obtained.
- the carbon content from the surface to 0.1 ⁇ m to 0.5 ⁇ m needs to be 10 at% or more.
- a titanium plate is annealed as needed after hot-rolling a titanium cast piece, and also it cold-rolls and is manufactured.
- the titanium plate according to the present invention can be manufactured by performing a first step and a second step described below in cold rolling. Further, after the cold rolling, a final annealing step (third step) or shape correction may be performed as necessary.
- intermediate annealing may be required depending on the thickness of the hot rolled sheet and the thickness of the product.
- the intermediate annealing at this time is performed in a continuous or batch manner within a range of 600 to 800 ° C.
- the atmosphere is a vacuum or an Ar gas atmosphere, but in the case of the continuous type, the atmosphere may be carried out in the air, and after annealing in the air, descaling by pickling is necessary. After descaling, the final rolling process (final cold rolling process) is performed.
- the surface is removed by pickling when the intermediate annealing is performed in the air, carbon and the like attached to the surface by rolling so far are also removed. Of course, carbon remains on the surface in a vacuum or Ar gas atmosphere.
- intermediate annealing is often required. However, when using a hot-rolled sheet having a thickness of more than 0.3 mm and not more than 1.5 mm, intermediate annealing is not necessary.
- the first step is a step aimed at forming irregularities on the surface.
- the first step is a rolling pass excluding the final pass in the final cold rolling step performed on the hot-rolled sheet or the titanium plate after the intermediate annealing, or a rolling pass excluding the final pass and the pass before that one pass. . That is, the first step means from the 1st to (N-1) or 1st to (N-2) th pass in the N-pass final cold rolling step.
- the second step is a step aiming at final adjustment of unevenness and shape correction of the plate.
- the last two passes are the second step.
- the rolling reduction is high, and the rolling is performed at a rolling reduction of about 20% or less per pass.
- the rolling reduction is performed at about 10% or less per pass.
- the last pass of the first step or the last two passes two passes before the final pass in the final cold rolling step or two passes and three passes before the final pass for the hardened plate. ) Under strong pressure.
- a strong reduction is performed in the (N-2) th pass in the final cold rolling process of the Nth pass.
- strong reduction is performed in the (N-2) th and (N-3) th passes in the final cold rolling process of the Nth pass.
- the rolling is 20% or less. That is, it is sufficient that the maximum inter-pass reduction ratio of the last two passes in the first step is 15% or more.
- a rolling roll (surface control roll) having a large surface roughness such as a dull roll is used, the shape of the roll is transferred to the plate.
- the shape is not deeper than the target uneven shape, the shape is reduced by being crushed during shape correction. Therefore, it is necessary to apply a strong pressure here, too, and it is necessary to sufficiently transfer the irregularities on the roll surface to the plate surface. Therefore, it is preferable to use a roll in which the number density of the convex portions and the concave portions is 30 pieces / mm or more and the average interval (concave / convex width) between the convex portions and the concave portions is 20 ⁇ m or less in this scene under strong pressure. .
- the final adjustment of the unevenness and the shape correction of the plate are performed in the final pass in the final cold rolling step or in the previous pass. This is performed for the purpose of correcting the shape that has deteriorated due to the strong pressure (15% or more rolling reduction) performed in the first step and adjusting the uneven shape formed in the first step.
- Deteriorated shapes are exemplified by the waviness of the plate and the occurrence of wrinkles. Adjusting the uneven shape means that the number of uneven portions is mainly reduced by lowering the uneven portion formed in the first step by reducing the second step (less than 0.1 ⁇ m). To do.
- the uneven width is also affected, but not as high as the number density.
- Ra is preferably 0.4 ⁇ m or less.
- the surface roughness of the plate after rolling is not necessarily the surface roughness of the roll, Ra should be 0.4 ⁇ m or less as much as possible.
- the Ra lower limit is 0.05 ⁇ m
- 0.05 ⁇ m is a desirable lower limit for the roughness of the roll.
- FIG. 4 shows the rolling reduction between each pass.
- the pass schedule in FIG. 4 is an example in which a hot-rolled sheet is cold-rolled to 1 mmt, then subjected to atmospheric annealing at 700 ° C. for 2 minutes, and descaled by pickling.
- the initial rolling reduction increases and decreases as rolling progresses.
- triangular plot “ ⁇ ” strong reduction of 15% is performed two passes before the seventh pass (seventh pass), which corresponds to the first step.
- the final two passes (8th pass and 9th pass) have a low rolling reduction, and the shape correction is performed to reduce the shape change in the first step, which corresponds to the second step.
- the surfaces of the roll and the titanium plate are in uniform contact and uniform processing is applied in any pass rolling. This is because when the roll and the titanium plate are in local contact, the deformation becomes non-uniform due to the difference in the degree of processing from the periphery, which may cause a defective shape in rolling. In addition, when not uniformly processed, unevenness due to the formed cracks is also unevenly distributed, and it is difficult to obtain unevenness with a desired number density and average interval, such as an increase in depth.
- the rolling oil is uniformly distributed on the surface of the titanium plate, and the viscosity and supply amount of the rolling oil are appropriately controlled. That's fine.
- the rolling oil may be a general cold rolling oil (mineral oil), and its kinematic viscosity (40 ° C.) is about 8 to 15 mm 2 / s.
- the supply amount only needs to be supplied over the entire contact width when the material to be rolled comes into contact with the rolling roll, and is preferably set according to the supply method (supply position, number of supply ports, etc.).
- the annealing in the third step may be a continuous type or a batch type, and may be an inert atmosphere (for example, BA: Bright Annealing). However, when the plate thickness is thin, particularly when it is less than 0.3 mm, the annealing must be performed continuously. In the batch type, the coil is placed on the hearth and annealed, so that the edge buckles and the shape is greatly impaired.
- the annealing temperature is preferably 600 ° C. or higher in order to obtain formability.
- the annealing temperature is less than 600 ° C., the processed structure remains and the formability of the titanium plate is lowered.
- the upper limit of the annealing temperature is 800 ° C. The reason is that when the temperature exceeds 800 ° C., carbon diffuses to expand the hardened region of the surface layer, and the workability deteriorates.
- a preferable range of the annealing time is 30 s to 2 min.
- Shape correction Warping may occur due to the effect of tension during annealing. In that case, shape correction is performed after annealing. In that case, care is taken to obtain a predetermined surface (irregularity of a desired number density and average interval), and this is performed as necessary.
- the thickness of the titanium plate according to the present invention is exemplified by 0.05 to 1.0 mm.
- the film formed on the surface of the titanium plate according to the present invention is formed on the surface on which the irregularities are formed as described above.
- the coating is selected according to the purpose, and is formed, for example, on a titanium plate processed into a predetermined shape. When used in the state of a flat plate, a film is formed on the surface of the titanium plate cut into a predetermined size.
- a titanium plate having alkali resistance equivalent to that of Ni or resin can be manufactured by coating the surface of the titanium plate with Ni or resin that is resistant to alkaline environment.
- a diaphragm with controlled sound quality can be manufactured by controlling the damping capacity.
- the thermal conductivity of a conventional titanium plate can be improved by coating these on the surface of the titanium plate.
- the heat resistance of the titanium plate can be improved by coating the surface of the titanium plate with a material having a low thermal conductivity such as zirconia. Further, by coating the surface of the titanium plate with hard ceramics, the wear resistance of the titanium plate can be improved.
- Forming Method of Coating Films may be formed by any method such as PVD (Physical Vapor Deposition) method, CVD (Chemical Vapor Deposition) method, paste coating and baking method. It is effective to clean the surface of the titanium plate before the coating is formed. This is to prevent the material adhering to the surface from being gasified at the interface between the coating film on the surface and the base material and becoming the starting point of peeling.
- PVD Physical Vapor Deposition
- CVD Chemical Vapor Deposition
- paste coating paste coating and baking method. It is effective to clean the surface of the titanium plate before the coating is formed. This is to prevent the material adhering to the surface from being gasified at the interface between the coating film on the surface and the base material and becoming the starting point of peeling.
- the conditions in the examples are one example of conditions used for confirming the feasibility and effects of the present invention, and the present invention is based on this one example of conditions. It is not limited. As described above, the present invention can adopt various conditions as long as the object of the present invention is achieved without departing from the gist of the present invention.
- each titanium plate No. Chemical compositions of Nos. 1 to 55 (Nos. 1 to 30, 45 to 52 are examples of the present invention, Nos. 31 to 44 and 53 to 55 are comparative examples) are shown.
- the chemical composition is a component of the cold-rolled sheet after annealing.
- each titanium plate No. Production conditions 1 to 55 are shown.
- each titanium plate No. The evaluation results of 1 to 55 are shown.
- the total reduction rate (%) described in the right column of the second step is the sum of the total reduction rate (%) in the first step and the total reduction rate (%) in the second step.
- a value obtained by subtracting the total reduction rate (%) in the first step from the total reduction rate (%) described in the right column of the second step is the total reduction rate (%) in the second step.
- the material of the roll may be any of general high-speed steel, die steel, cemented carbide, etc., and the surface may have a coating such as CrN.
- a carbide roll was used. Moreover, after performing the 1st process, when the 2nd process was performed using the roll as it was, without re-polishing a roll, the surface of the roll was in the state coated with titanium. Thereafter, the cold-rolled plate was washed with alkali to remove oil on the surface, and then annealed at 600 to 800 ° C. for a maximum of 10 minutes (third step) in an Ar atmosphere.
- the column of final annealing shows annealing temperature, annealing time, and method (BA: Bright Annealing, AP: annealing and pickling). Tables 3 and 4 show the presence / absence of shape correction and the surface roughness Ra of the roll used for shape correction.
- the annealed cold-rolled sheet was cut into 4 cm square, and coated with a Ni, AlN, C thin film as a surface coating layer to a thickness of 2 ⁇ m.
- a film forming method a sputtering method which is a kind of PVD method was used. Further, a two-component epoxy resin (E) and a conductive epoxy (AE) added with silver as a thin film were applied to the surface and cured. However, the film thickness of the epoxy resin was 100 to 200 ⁇ m. In the column of the film adhesion film in Table 3, each titanium plate No. For 1 to 55, the type of coating was described.
- each titanium plate No. 1 to 55 Nos. 1 to 30, 45 to 52 are examples of the present invention, Nos.
- the evaluation of film adhesion was evaluated as A for the case where there was no peeling from the substrate, as B for evaluation of 10 or less peeled eyes, and as evaluation C for 11-20 peeled eyes. 21 to 30 were evaluated as D, and 31 or more peeled eyes were rated as E. A, B, and C are acceptable, and D and E are unacceptable.
- the Eriksen test uses a 90 mm square test piece with a wrinkle holding force of 10 kN, a Teflon sheet with a thickness of 50 ⁇ m (“Teflon” is a registered trademark), and a punch stroke speed of 20 mm / min up to a protruding height of 8 mm. After that, it was performed at 5 mm / min until breakage.
- the surface roughness is the arithmetic average roughness Ra defined in JIS B 0601: 2001.
- the number density and average interval of the surface irregularities are the conditions described above with reference to FIGS.
- the roll roughness is the result of measurement after polishing the same material as the roll under the same conditions as roll polishing.
- the surface hardness (Vickers hardness) was measured at 10 points randomly so that the indentations were separated by a distance of 5 or more indentations on the plate surface with a load of 25 gf, and the average value was evaluated.
- XPS was measured by the average carbon content at a depth of 0.1 to 0.5 ⁇ m from the surface at a SiO 2 conversion distance.
- the intensity is represented by the intensity ratio when the intensity of the characteristic X-ray K ⁇ of the standard sample (graphite) is 100%.
- the measurement area was 500 ⁇ m ⁇ 500 ⁇ m.
- the evaluation result in five stages does not change even if any thin film of Ni, AlN, C, epoxy resin (E) or conductive epoxy (AE) is coated. It was. That is, according to the titanium plate according to the present invention, good adhesion can be obtained for any metal film, ceramic film, or non-metal such as carbon.
- the adhesion of the surface coating layer in the present invention is obtained by an anchor effect due to a predetermined uneven shape on the surface, it is formed not only by the sputtering method used in this embodiment, but also by a plating method or a CVD method. Adhesion can also be improved in the surface coating layer.
- No. Nos. 12 and 13 are rolls controlled to a surface with a number density of 30 to 100 pieces / mm and a width of 20 ⁇ m or less, although the inter-pass rolling reduction rate of the pass immediately before finishing in the first step is less than 15%. The predetermined irregularities could be obtained.
- the number density of the unevenness on the surface greatly affects the adhesion, and when this number density is 30 or more, the adhesion is excellent. However, no. Although the number density of 31 to 33 is 30 or more, it exceeds 100 and the Erichsen value is low. This is because the surface carbon is increased by rolling at a reduction ratio that is too high in the first step, and the surface hardness is excessively increased accordingly. In particular, when the surface crack number density is large, the rolling oil tends to remain in the gap, and a large amount of rolling oil remains even after passing through the cleaning process. As a result, the surface hardens at the time of annealing because there is more carbon than the amount of carbon attached to the surface by rolling.
- No. Nos. 34 to 38 were inferior in adhesion because the number density and / or uneven width was out of a predetermined range because the rolling reduction ratio immediately before finishing in the first step was less than 15%.
- No. Nos. 39 to 41 were subjected to atmospheric annealing (AP) in the third step and pickled, so that a predetermined surface state was not obtained and adhesion to the film was inferior.
- No. No. 42 has a low Erichsen value due to its high oxygen content.
- No. 53 had a low Erichsen value due to the high iron content.
- No. 54 has a low Erichsen value due to its high nitrogen content.
- No. No. 55 had a low Erichsen value due to its high carbon content.
- No. No. 43 has a surface roughness of the rolling roll used in the second step of less than 0.05 ⁇ m, and Ra of the obtained titanium plate is also less than 0.05 ⁇ m.
- the number density of unevenness effective for the anchor effect is 30 pieces. Since it was less than / mm, the adhesion with the film was inferior.
- No. No. 44 has a final plate thickness of 0.3 mm or less, and the total rolling reduction in the final cold rolling process exceeded 80%. Therefore, the Erichsen value was affected by the cracks on the surface that became deep due to the thin plate thickness. Less than 10 mm.
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Abstract
Description
Fe:0.00~0.20%、
O:0.00~0.12%、
N:0.00~0.08%、
C:0.00~0.10%、
H:0.000~0.013%、
Al:0.00~0.50%、
Cu:0.00~0.50%、
Si:0.00~0.30%、
Cr:0.00~0.50%、
Ni:0.00~0.50%、
Mo:0.00~0.50%、
V:0.00~0.50%、
Nb:0.00~0.50%、
Sn:0.00~0.50%、
Co:0.00~0.50%、
Zr:0.00~0.50%、
Mn:0.00~0.50%、
Ta:0.00~0.50%、
W:0.00~0.50%、
Hf:0.00~0.50%、
Pd:0.00~0.50%、
Ru:0.00~0.50%、
残部Tiおよび不純物である化学組成を有し、
表面の算術平均粗さRaが0.05μm以上0.40μm以下であり、前記表面にX線回折から得られるチタン炭化物に起因する積分強度総和Icと、チタン炭化物およびチタンに起因するすべてのピークの積分強度総和Imとの比((Ic/Im)×100)が0.8%以上5.0%以下であるチタン炭化物を有し、前記表面の凹凸の数密度が30~100個/mmであるとともに、前記凹凸の平均間隔が20μm以下である、チタン板。
本実施の形態に係るチタン板の化学組成は、質量%で、Fe:0.20%以下、O:0.12%以下、N:0.08%以下、C:0.10%以下、H:0.013%以下、残部Ti及び不純物からなるもの、ということができる。以下に説明する化学組成に関する「%」は、特に断りがない限り「質量%」を意味する。
Fe含有量が多くなるとβ相を生じ、それによって微細な組織が得られるために加工性が損なわれる。このため、Fe含有量は、0.20%以下であり、望ましくは0.15%であり、より望ましくは0.10%以下である。一方、Fe含有量の下限は、0.00%である。しかし、Feの含有は工業的に不可避であるため、Fe含有量の下限は0.01%、0.02%、又は0.03%であってもよい。
Oは、チタン板の強度を高める反面、加工性を大きく低下させる。このため、O含有量は、0.12%以下であり、望ましくは0.10%以下であり、より望ましくは0.08%以下である。一方、O含有量の下限は、0.00%である。しかし、Oの含有は工業的に不可避であるため、O含有量の下限は0.01%、0.02%、又は0.03%であってもよい。
Nも、Oと同様にチタン板の加工性を低下させる。このため、N含有量は、0.08%以下であり、望ましくは0.05以下であり、より望ましくは0.03以下である。一方、N含有量の下限は、0.00%である。しかし、Nの含有は工業的に不可避であるため、N含有量の下限は0.01%、0.02%、又は0.03%であってもよい。
Cは、OやNよりも強度や加工性に及ぼす影響は小さい。しかし、OやNが含有されることを考慮すると、C含有量の上限は0.10%であり、望ましくは0.08以下であり、より望ましくは0.03以下である。一方、C含有量の下限は、0.00%である。しかし、C含有量の下限は工業的に不可避であるため、C含有量の下限は0.01%、0.02%、又は0.03%であってもよい。
Hは、脆化を引き起こす元素であり、室温での固溶限は10ppm前後であるため、これ以上のHが含有される場合には水素化物が形成され、脆化することが懸念される。一般的に、含有量が0.013%以下であれば、脆化の懸念はあるものの実用上問題なく用いられている。好ましくは0.010%以下であり、さらに好ましくは0.008%以下、0.006%以下、0.004%以下または0.003%以下である。H含有量の下限は0.000%である。必要があれば、その下限は0.001%、0.002%、又は0.003%であってもよい。
原料としてスクラップの利用を促進すると、上述の元素(Fe、O、N、C、H)に加えて、これらの元素以外の金属元素が混入する。厳格な管理をすればこれらの元素の混入は防ぐことができるものの、その処理コストが嵩む。本発明では、安価なチタン板を提供するために、スクラップに由来する金属元素の混入を本発明の効果を阻害しない範囲で可能な限り許容する。スクラップに由来する金属元素には、Al,Cu,Cr,Ni,Mo,V,Sn,Co,Zr,Nb,Si,Mn,Ta,W,Hf,Pd,Ruなどがある。
Alは、β相の生成を促進しないものの、加工性を低下させる。このため、Al含有量は、0.50%以下であり、望ましくは0.40%以下であり、さらに望ましくは0.30%以下である。
Cuは、Alほど加工性を低下させない。このため、Cu含有量は0.50%以下であり、望ましくは0.40%以下であり、さらに望ましくは0.30%以下である。
SiはAlよりも加工性への影響が大きいため、Si含有量は、0.30%以下であり、望ましくは0.20%以下であり、さらに望ましくは0.15%以下である。
Cr,Ni,Mo,V,Nbは、Feと同様にβ相の生成を強く促進する。このため、Cr,Ni,Mo,V,Nbの含有量は、それぞれ、0.50%以下であるとともに、Cr,Ni,Mo,V,Nbの合計含有量は、1.00%以下であり、望ましくは0.80%以下であり、より望ましくは0.60%以下である。
Sn,Co,Zr,Mn,Ta,W,Hf,Pd,Ruは、Alほど加工性を低下させない。このため、Sn,Co,Zr,Mn,Ta,W,Hf,Pd,Ruの含有量は、それぞれ0.50%以下とするとともに、合計含有量は、1.00%以下であり、望ましくは0.80%以下であり、さらに望ましくは0.60%以下である。
上記以外の残部はTiおよび不純物である。
後述するように、チタン板の表面の凹凸の数密度および幅を制御したとしても、その深さが深い場合(高低差が大きい場合)には、応力集中の起点となり、破壊に至る。また、チタン板への表面処理を施す際に平滑な面を得ることも難しくなる。このため、チタン板の表面の粗さは小さくしておくことが有効である。このような観点から、本発明に係るチタン板の表面の算術平均粗さRaは、0.40μm以下であり、より望ましくは0.30μm以下である。また、下限はアンカー効果が十分得られるように0.05μm以上である。算術平均粗さRaはJIS B 0601:2001に規定される値であり、チタン板の圧延面において圧延方向に垂直な方向に測定した実表面の断面曲線から求められる。その手順は、まず、波長408nmのバイオレットレーザを用いたレーザ式測定装置で測定倍率500倍(視野は約300μm角)、Z方向0.1μmピッチ、ビーム径0.1μm以下で測定した断面曲線についてカットオフ値λc=0.08mmのフィルタによって粗さ曲線とした。得られた粗さ曲線について、算術平均粗さRaを求めた。なお、この時の評価長さ(基準長さ)は約300μm(正確には298μm)である。また、1視野の測定ではばらつきが生じる場合があるため、5箇所(視野)の測定値の平均値を用いた。
図1は、本発明に係るチタン板の表面における粗さ曲線の一例を示す説明図である。
アンカー効果に有効な凹凸を効果的に形成させるため、凹凸形成前に炭素による表面硬化が行われることが好ましい。このため、上記の凹凸の数密度や凹凸幅を得た凹凸形成後のチタン板の表面には、板厚中央部よりも炭素が多く含まれることになる。例えば、チタン板の表面から深さ0.1μm~1.0μmの領域に平均で10at%以上の炭素を含有していることが好ましい。この領域の炭素は、平均で、12atm%以上、15atm%以上、17atm%以上でもよい。又、この領域の炭素は、平均で、32atm%以下、30atm%以下、28atm%以下でもよい。炭素量の分析は、スパッタリングとXPS(X-ray photoelectron spectroscopy)による元素量測定を複数回繰り返すことで行われる。なお、XPSにおける深さ位置はArイオンによってSiO2がスパッタされる距離で管理するため、このSiO2換算距離で表面から0.1μm~0.5μmまでの深さにおいて平均炭素量が10atm%以上であればよい。詳細には、表面からSiO2換算距離で0.1μmの深さまでArスパッタ(スパッタ速度:SiO2換算で1.9nm/min)を行い、単色化Al Kα線をビーム直径200μmで試料表面(0.1μmの深さまでスパッタされた表面)に照射し、それによって得られる光電子を用いて炭素量を測定し、その後はSiO2換算距離0.1~0.2μmピッチで表面からSiO2換算距離で深さ0.5μmまでスパッタと測定を繰返し、各深さで得られた炭素量の平均値を求める。なお、炭素以外の元素は窒素、酸素、チタンを必須とし、定性分析で検出された元素についても、同様に測定する。チタン板の表層の炭素は、圧延油から供給され、表層に対する冷間圧延によってチタン板の極表層(例えば、表面から深さ1μm以下の範囲)のみに導入される。固溶強化は炭素の固溶量、加工硬化は加工量、によって硬化の程度は異なる。加工硬化では軟質な部分に変形が集中するため、軟質部が優先的に硬化する。しかし、加工硬化だけでは十分に均一な効果をしないため、炭素やチタン炭化物などによって軟質部を減らすことで、加工硬化でさらに軟質部を減らすことができる。そのため、表層に存在する炭素による固溶強化により、チタン板の表層は高強度化するとともに、加工されることにより表層は加工硬化し、チタン板の表層に形成されるチタン炭化物との相乗効果によってほぼ均一に硬質化する。
なお、冷間圧延ままでは凸部の頂点近傍にTiCxが存在し、凹部には存在していない。しかし、洗浄で除去できない圧延油が凹部に残存し、焼鈍でTiCxを形成する。また、焼鈍では炭素が内部に拡散するため、大圧下によって凹凸を形成したときの炭素分布と焼鈍後の炭素分布は異なっている。密着性に有効な凹凸が0.1μm以上であることから、板表面から0.1μm以上の領域に十分な炭素が存在しなければ冷間圧延時に所望の凹凸を形成させられない。さらに炭素が焼鈍によって拡散することも考慮すると、焼鈍後の表面から0.1μm~0.5μmの炭素量を評価し、その値が10at%以上の場合に、所望の凹凸が得られていたために、表面から0.1μm~0.5μmの炭素量は10at%以上である必要がある。
チタン板は、チタン鋳片を熱間圧延後、必要に応じて焼鈍し、さらに冷間圧延して製造される。本発明に係るチタン板は、冷間圧延において、以下に説明する第1工程と第2工程を行うことにより、製造することができる。また、冷間圧延後に、さらに必要に応じて最終焼鈍工程(第3工程)や形状矯正を行っても良い。
第1工程は表面の凹凸形成を目的とする工程である。第1工程は、熱延板もしくは中間焼鈍後のチタン板に対して行う最終冷間圧延工程における最終パスを除いた圧延パス、もしくは最終パスとその1パス前のパスを除いた圧延パスである。すなわち、第1工程は、Nパスの最終冷間圧延工程において、1から(N-1)もしくは1から(N-2)パス目までを意味している。第2工程は、凹凸の最終調整と板の形状矯正を目的とする工程である。1パス目から(N-1)パス目までが第1工程となる場合、最終冷間圧延工程の最終パス(Nパス目)のみが第2工程となる。一方、(N-2)パス目を第1工程とする場合は、最終2パス(N-1パス目、Nパス目)が第2工程となる。一般的な冷間圧延では、初期パスは軟質であるため、圧下率が高く、1パス当たり20%以下程度の圧下率で行われる。更に圧延が進むと、加工硬化によって硬質化するとともに、板厚が薄くなることで良好な形状を保つことが難しくなるため、圧下率は1パス当たり10%以下程度で行われる。一方、本発明では硬質化した板に対する、第1工程の最後の1パスもしくは最後の2パス(最終冷間圧延工程の中の最終パスの2パス前もしくは最終パスの2パス前および3パス前)において強圧下を行う。すなわち、Nパスの最終冷間圧延工程における(N-2)パス目に強圧下を行う。もしくは、Nパスの最終冷間圧延工程における(N-2)パス目及び(N-3)パス目に強圧下を行う。ここでの強圧下はパス間の圧下率15%以上とする必要がある。なお、過度な割れを発生させないためには20%以下の圧延であることが好ましい。すなわち、第1工程の最終2パスの最大パス間圧下率が15%以上であればよい。また、ダルロールなどの表面粗さが大きな圧延ロール(表面制御ロール)を用いる場合、ロールの形状が板に転写されるため、本発明で板に形成したい凹凸形状にしておく。狙いの凹凸形状よりも深い形状にしておかなければ、形状矯正時に圧下されることで浅くなるためである。そのため、ここでも強圧下する必要があり、十分にロール表面の凹凸を板表面に転写する必要がある。そのため、この強圧下の場面では、凸部及び凹部の数密度が30個/mm以上であり、かつ凸部及び凹部の平均間隔(凹凸幅)が20μm以下になっているロールを用いることが好ましい。
冷間圧延で形成した表面(凹凸)を維持するために、表面状態を維持することができる焼鈍方法を選択することが有効である。第3工程での焼鈍は、連続式でもよくバッチ式でもよく、不活性雰囲気(例えば、BA:Bright Annealing)であればよい。ただし、板厚が薄い場合、特に0.3mmを下回る場合には連続式で焼鈍を行わなければならない。バッチ式ではコイルを炉床に置いて焼鈍するため、エッジが座屈して形状が大きく損なわれるためである。焼鈍温度は、成形性を得るために600℃以上で行うことが好ましい。焼鈍温度が600℃未満であると、加工組織が残存してチタン板の成形性が低下する。焼鈍温度は、800℃を上限とする。その理由は、800℃を超えると、炭素が拡散して表層の硬化領域が広がり、加工性が劣化するためである。焼鈍時間は、30s~2minが好適な範囲である。
焼鈍時に張力等の影響で反りが生じたりする場合がある。その場合には焼鈍後に形状矯正を行う。その場合、所定の表面(所望の数密度及び平均間隔の凹凸)を得られるように注意して、必要に応じて実施する。なお、本発明に係るチタン板の板厚は0.05~1.0mmが例示される。
本発明に係るチタン板の表面に形成する被膜は、上述のように凹凸が形成された表面に形成される。被膜は、目的に応じて選択され、例えば所定の形状に加工したチタン板に形成される。平板の状態で使用される場合には、所定サイズに切断されたチタン板の表面に被膜が形成される。
被膜の形成は、PVD(Physical Vapor Deposition)法やCVD(Chemical Vapor Deposition)法、ペースト塗布およびベーキング法などいずれの方法でもよい。被膜の形成前にチタン板の表面を洗浄することが有効である。これは、表面に付着している物質によって表面の被膜と母材との界面でガス化したり、はく離の起点になることを防ぐためである。
Claims (5)
- 質量%で、
Fe:0.00~0.20%、
O:0.00~0.12%、
N:0.00~0.08%、
C:0.00~0.10%、
H:0.000~0.013%、
Al:0.00~0.50%、
Cu:0.00~0.50%、
Si:0.00~0.30%、
Cr:0.00~0.50%、
Ni:0.00~0.50%、
Mo:0.00~0.50%、
V:0.00~0.50%、
Nb:0.00~0.50%、
Sn:0.00~0.50%、
Co:0.00~0.50%、
Zr:0.00~0.50%、
Mn:0.00~0.50%、
Ta:0.00~0.50%、
W:0.00~0.50%、
Hf:0.00~0.50%、
Pd:0.00~0.50%、
Ru:0.00~0.50%、
残部Tiおよび不純物である化学組成を有し、
表面の算術平均粗さRaが0.05μm以上0.40μm以下であり、前記表面にX線回折から得られるチタン炭化物に起因する積分強度総和Icと、チタン炭化物およびチタンに起因するすべてのピークの積分強度総和Imとの比((Ic/Im)×100)が0.8%以上5.0%以下であるチタン炭化物を有し、前記表面の凹凸の数密度が30~100個/mmであるとともに、前記凹凸の平均間隔が20μm以下である、チタン板。 - 質量%で、Cr+Ni+Mo+V+Nb:0.00~1.00%である、請求項1のチタン板。
- 質量%で、Sn+Co+Zr+Mn+Ta+W+Hf+Pd+Ru:0.00~1.00%である、請求項1のチタン板。
- 前記表面から深さ0.1μm~0.5μmの表層において、XPSを用いて測定される炭素含有量が10.0at%以上である、請求項1に記載のチタン板。
- 加速電圧10kVでのEPMAによって得られる前記表面からの特性X線(Kα線)強度と、グラファイトにおけるKα線強度との比が1.00%以上である、請求項1に記載のチタン板。
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EP18913854.8A EP3778046A4 (en) | 2018-04-03 | 2018-04-03 | TITANIUM PLATE |
US17/041,806 US11566305B2 (en) | 2018-04-03 | 2018-04-03 | Titanium plate |
KR1020207029457A KR102404467B1 (ko) | 2018-04-03 | 2018-04-03 | 티타늄판 |
CN201880091873.4A CN111902222B (zh) | 2018-04-03 | 2018-04-03 | 钛板 |
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