Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C1/00—Making non-ferrous alloys
  • C22C1/10—Alloys containing non-metals
  • C22C1/1026—Alloys containing non-metals starting from a solution or a suspension of (a) compound(s) of at least one of the alloy constituents
• • 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
• • 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
  • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
  • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment

Definitions

• the present invention relates to a titanium material and a method for manufacturing a titanium material.
• Titanium material used for building materials such as walls and roofs of buildings is an uncolored material that has a silver color, which is the color of titanium itself, and anodizing to a certain thickness on the surface. By applying a film, it exhibits an interference color such as red or blue, and is roughly classified into a coloring material with a design property.
• Titanium material is also used as a building material in beach areas where salt adheres due to its excellent corrosion resistance. It has been more than 20 years since titanium was first used as a building material, but there have been no reports of problematic corrosion. Both the uncolored material and the colored material show excellent corrosion resistance.
• Both uncolored and colored materials may discolor when exposed to the atmosphere for a long period of time. It has been clarified that this discoloration is an interference color caused by an increase in the oxide film on the surface of the titanium material to a thickness of about several tens of nm due to an acidic environment having a pH of 4.5 or less, for example, acid rain. .. Such an oxide film of about several tens of nm does not impair the corrosion resistance of titanium.
• titanium materials that are less likely to cause interference color due to an increase in the thickness of the oxide film, especially uncolored materials are required in parts such as walls and roofs of buildings where the appearance is important. Material development is underway.
• Patent Document 1 is characterized in that the average carbon concentration in the depth range of 100 nm from the outermost surface is 14 atomic% or less, and the outermost surface has an oxide film having a thickness of 12 to 40 nm.
• a titanium material that is less likely to cause discoloration in the atmospheric environment is disclosed.
• Patent Document 2 discloses a titanium material that is less likely to cause discoloration, characterized in that the amount of fluorine in the oxide film on the surface is 7 atomic% or less.
• x is 0.8 when the composition of the titanium oxide is TiO x in the oxide film existing in the range from the titanium surface to 3 nm.
• a titanium material which is in the range of about 1.8 and has a density of the oxide film of 4.2 g / cm 3 or more, which is less likely to cause discoloration in the air environment.
• the titanium material disclosed in Patent Document 3 is produced by a method of treating the titanium surface with a mixed solution of nitric acid and hydrofluoric acid and then treating with a nitric acid solution or the like.
• Patent Document 4 describes a pure titanium material used as a building material, in which Fe as an impurity element is suppressed to 0.08% by mass or less, Nb is suppressed to 0.02% by mass or less, and Co is suppressed to 0.02% by mass or less.
• a pure titanium material for building materials which is characterized by the fact that it is used, is disclosed.
• the titanium material disclosed in Patent Document 4 is produced by heating at 130 to 280 ° C. for a predetermined time in the air or vacuum following a pickling treatment in the final step.
• the uncolored material is required to have high weather resistance that does not cause interference color. Further, in recent years, there has been a demand for a titanium material which is less likely to cause discoloration even in an acidic environment having a pH of 3.0 or less, which is more severe than the above, under an increase in temperature due to changes in the atmospheric environment.
• Patent Documents 1 to 4 the evaluation of weather resistance is as follows. It is immersed in a sulfuric acid aqueous solution having a pH of 3 to 4 at 60 ° C. for several days, and the weather resistance is evaluated by the color difference before and after the immersion. The color difference is 3 to 7 or less when immersed in a sulfuric acid aqueous solution of pH 3 at 60 ° C. for 7 days or 14 days, and the color difference is less than 5 when immersed in a sulfuric acid aqueous solution of pH 4 at 60 ° C. for 3 days. It is described as less than 1. However, the above weather resistance evaluation does not sufficiently reflect the use in a high temperature environment.
• Patent Documents 1 to 4 when the titanium materials described in Patent Documents 1 to 4 are immersed in a sulfuric acid aqueous solution at 80 ° C. and pH 4 for 4 days, the color difference before and after the immersion is about 15 or more, and the conventional titanium material has a higher temperature. Under the conditions, it does not have sufficient weather resistance.
• the present invention has been made in view of the above problems, and an object of the present invention is to provide a titanium material having excellent weather resistance and an efficient method for producing the titanium material.
• the present inventors have found that the surface oxide film has excellent weather resistance when a specific element is contained. .. Then, the present inventors have found that the elemental content of the surface oxide film can be controlled by a cleaning step using nitric acid. Furthermore, it was newly found that weather resistance in an acidic environment can be obtained by carrying out the above cleaning step in the final step. The present inventors have reached the present invention as a result of further studies based on the obtained findings.
• the gist of the present invention completed based on the above findings is as follows.
• the surface composition is Zn: 0.1 atomic% or more and Ca: 0. It is characterized by containing 5 atomic% or more and having a surface oxide film composition of C: 20.0 atomic% or less and F: 5.0 atomic% or less.
• the titanium material according to the above [1] may have a surface oxide film having a thickness of 5 to 20 nm.
• the method for producing a titanium material according to another aspect of the present invention includes a cleaning step of cleaning the titanium material, and the cleaning step is 0.00030 to 0.65000 in terms of zinc salt: Zn. Weight%, calcium salt: 0.00060 to 0.40000% by mass in terms of Ca, HF: 1.0 to 6.0% by mass, and HNO 3 : 4.0 to 10.0% by mass. It includes a dipping treatment in which the titanium material is immersed in an aqueous solution having a temperature of 40 to 60 ° C. for 1.0 minute or more, and a water washing treatment in which the titanium material pulled up from the aqueous solution is washed with water.
• the zinc salt 0.00030 to 0.00100% by mass in terms of Zn and the calcium salt: 0.00060 to 0.00108% by mass in terms of Ca. , May be.
• the zinc salt may be ZnCl 2 .
• the calcium salt may be CaCl 2 .
• the calcium salt may be CaCl 2 .
• the method for producing a titanium material according to the above [3] or [4] may further include a heating step of heating the titanium material after the cleaning step to 300 to 900 ° C. under an inert atmosphere. .. [9]
• the method for producing a titanium material according to the above [5] may further include a heating step of heating the titanium material after the cleaning step to 300 to 900 ° C. under an inert atmosphere.
• the method for producing a titanium material according to the above [6] may further include a heating step of heating the titanium material after the cleaning step to 300 to 900 ° C. under an inert atmosphere.
• the method for producing a titanium material according to the above [7] may further include a heating step of heating the titanium material after the cleaning step to 300 to 900 ° C. under an inert atmosphere.
• Titanium material includes a titanium bulk material (titanium base material) and a surface oxide film arranged on the surface of the titanium bulk material.
• the titanium material according to this embodiment will be described in detail below.
• the titanium bulk material in the titanium material of the present embodiment is made of either pure titanium or a titanium alloy.
• the titanium bulk material is, for example, pure titanium or a titanium alloy having a Ti content of 70% by mass or more.
• Pure titanium includes, for example, 1 to 4 types of JIS standard and industrial pure titanium specified by Grade 1 to 4 of ASTM standard corresponding to these. That is, the target industrial pure titanium in this embodiment is C: 0.1% or less, H: 0.015% or less, O: 0.4% or less, N: 0.07% or less in mass%. , Fe: 0.5% or less, the balance consists of Ti and impurities.
• JIS1 type and its equivalent ASTMGr Pure industrial titanium specified in 1 or its equivalent is mainly used.
• titanium alloy examples include ⁇ -type titanium alloy, ⁇ + ⁇ -type titanium alloy, and ⁇ -type titanium alloy.
• the ⁇ -type titanium alloy is defined by, for example, a highly corrosion-resistant alloy (JIS standard 11 to 13, 17, 19 to 22 and ASTM standard Grade 7, 11, 13, 14, 17, 30, 31). Titanium alloy and titanium alloy containing a small amount of various elements), Ti-0.5Cu, Ti-1.0Cu, Ti-1.0Cu-0.5Nb, Ti-1.0Cu-1.0Sn-0 .3Si-0.25Nb, Ti-0.05 to 0.2Pd and the like.
• Examples of the ⁇ + ⁇ type titanium alloy include Ti-3Al-2.5V, Ti-5Al-1Fe, Ti-6Al-4V and the like.
• Examples of the ⁇ -type titanium alloy include Ti-11.5Mo-6Zr-4.5Sn, Ti-8V-3Al-6Cr-4Mo-4Zr, Ti-13V-11Cr-3Al, Ti-15V-3Al-3Cr-3Sn. , Ti-20V-4Al-1Sn, Ti-22V-4Al and the like.
• the surface composition when the chemical composition of the surface of the titanium material is analyzed by X-ray photoelectron spectroscopy, the surface composition is Zn: 0.1 atomic% or more and Ca: 0.5.
• the composition of the surface oxide film is C: 20.0 atomic% or less and F: 5.0 atomic% or less.
• the surface composition is Zn: 0.1 atomic% or more, Ca: 0.5 atomic% or more
• the Zn content of the surface is 0.1 atomic% or more
• the Ca content is 0. It is 0.5 atomic% or more.
• Zn and Ca on the surface of the titanium material improve the weather resistance of the titanium material.
• the inhibitor effect is an effect of suppressing the growth of the surface oxide film by suppressing the dissolution of titanium by preferentially dissolving Zn and Ca on the surface of the titanium material in an acid rain environment.
• the oxygen deficiency repair effect is as follows: Zn 2+ and Ca 2+ are doped at the Ti 4+ site of TiO 2 constituting the surface oxide film, and as a result of repairing the oxygen deficiency, the elution of titanium is suppressed and the surface oxide film is formed. It is an effect that suppresses the growth of.
• the bipolar film effect has the effect of precipitating oxides (ZnO, CaO) having different semiconductor characteristics from TiO 2 and hindering the movement of electrons from the acidic solution adhering to the surface of the surface oxide film and suppressing the growth of the surface oxide film.
• ZnO, CaO precipitating oxides
• the chemical composition of the surface of the titanium material is analyzed by X-ray photoelectron spectroscopy, the Zn content on the surface of the titanium material should be 0.1 atomic% or more, and the Ca content should be 0.5 atomic% or more.
• the Zn content is preferably 0.1 atomic% or more, 0.2 atomic% or more, and more preferably 0.3 atomic% or more.
• the Ca content is preferably 0.5 atomic% or more, 0.6 atomic% or more, and more preferably 0.7 atomic% or more.
• the Zn content is preferably 1.0 atomic% or less, the Ca content is preferably 1.5 atomic% or less, and when the Zn content and the Ca content are higher than these values, the above effects tend to be saturated. show.
• the Zn content is more preferably 0.9 atomic% or less.
• the Ca content is more preferably 1.4 atomic% or less, still more preferably 1.3 atomic% or less.
• C 20.0 atomic% or less, F: 5.0 atomic% or less
• the C content and F content in the surface oxide film are 20.0 atomic% or less and 5.0 atomic% or less, respectively. If the C content and F content of the surface oxide film are high, discoloration is likely to occur. This is because carbon, fluorine, or a compound thereof reduces the action of the surface oxide film that suppresses the elution of the titanium substrate, making it easier for titanium to elute, or it exists as a compound with titanium in the surface oxide film. This is because the surface oxide film grows due to the fact that the compound is easily dissolved.
• carbon and fluorine in the surface oxide film may exist alone or as a compound with titanium, hydrogen, oxygen and the like.
• the C content is 20.0 atomic% or less and the F content is 5.0 atomic% or less, the elution of titanium in the titanium material and the growth of the surface oxide film are suppressed.
• the C content is 18.0 atomic% or less, 15.0 atomic% or less, or 6.0 atomic% or less.
• the F content is 4.9 atomic% or less, 4.8 atomic% or less, 4.5 atomic% or less, or 4.0 atomic% or less. It is preferable that the C content and the F content of the surface oxide film are small, but in terms of production, the C content is substantially 0.5 atomic% or more, and the F content is 1.0 atomic% or more. Is. More preferably, the C atom is 1.0 atom% or more. The F content is more preferably 2.0 atomic% or more.
• the thickness of the surface oxide film can be, for example, 100 nm or less, more preferably 80 nm or less, and further preferably 5 nm or more and 20 nm or less. When the thickness of the surface oxide film is 20 nm or less, it is possible to suppress the generation of interference color due to the surface oxide film.
• the thickness of the surface oxide film is more preferably 18 nm or less, still more preferably 12 nm or less.
• the lower limit of the thickness of the surface oxide film is preferably 5 nm or more.
• the thickness of the surface oxide film is 5 nm or more, the elution of Ti contained in the titanium material is suppressed, and higher weather resistance can be obtained.
• the thickness of the surface oxide film is more preferably 6 nm or more.
• the thickness of the surface oxide film refers to the position from the surface of the surface oxide film to the position where the oxygen concentration is an intermediate concentration between the maximum concentration and the base concentration.
• the base concentration is the average oxygen concentration in the range where the oxygen concentration curve is flat in the range where the oxygen concentration is 5 atomic% or less by performing XPS analysis in the depth direction from the surface of the titanium material while performing sputtering. say.
• flat means a place where the slope of the approximate straight line is 0.002 or less in absolute value in an arbitrary depth range including a maximum of 5 points or more of the quantitative value of oxygen concentration measured by XPS analysis described later. Say.
• the formula for the approximate straight line is calculated by the method of least squares.
• the Zn content and Ca content, the F content and C content of the surface oxide film, and the thickness of the surface oxide film were obtained by XPS for the titanium material after being immersed in acetone and ultrasonically cleaned. It can be obtained from the composition distribution in the depth direction from the surface.
• the ultrasonic cleaning time may be, for example, 30 seconds or more.
• the quantitative analysis values of each element are obtained and used as the Zn content and Ca content.
• the Zn content and Ca content referred to here refer to the respective contents in the range of 8 nm or less from the surface of the sample in the state where sputtering is not performed.
• composition analysis in the depth direction quantitative analysis of each element is performed every 2 nm of sputtering depth in terms of SiO 2 , and F content, C content and O are performed from the surface of the titanium material to the depth where the oxygen concentration becomes the base concentration. Determine the content.
• the thickness of the surface oxide film is analyzed by XPS to a depth where a baseline with a flat oxygen concentration curve can be obtained in the range where the oxygen concentration is 5 atomic% or less, and the O content is halved with respect to the maximum value.
• the sputtering time at the position is obtained, and the value is obtained by multiplying the sputtering speed converted to SiO 2 by the above sputtering time.
• the SiO 2 equivalent sputtering speed is the sputtering speed obtained under the same measurement conditions using a SiO 2 film whose thickness has been measured in advance using an ellipsometer.
• the baseline can be obtained by analyzing up to a position of 50 nm from the surface, but depending on the surface condition of the titanium material, a baseline may be obtained by analyzing up to a position of 100 nm from the surface.
• the maximum fluorine concentration in the surface oxide film measured by the above method is defined as the F content in the surface oxide film.
• the oxygen concentration decreases near the surface of the titanium material for carbon whose concentration decreases almost monotonously in the depth direction.
• the C content is defined as the maximum value of the carbon concentration after the depth at which the oxygen concentration is maximized in the surface oxide film, considering that the portion where the carbon is attached is the effect of the adhered organic matter.
• the shape of the titanium material according to this embodiment is not particularly limited, and is a plate, a coil, a strip, or the like. Up to this point, the titanium material according to the present embodiment has been described.
• the present inventors have found that a titanium material having both weather resistance and whiteness in an acidic environment can be provided by carrying out a cleaning step including a dipping treatment using the above-mentioned vitreous acid in the final step.
• the whiteness L * on the surface of the titanium material is 70 or more.
• L * is preferably 90 or less.
• L * is 80 or less. It should be noted that this whiteness can be easily achieved by the cleaning step described later.
• the whiteness is measured by, for example, the following method. That is, according to JIS Z8730: 2009, L * is measured with a light source C using a colorimeter CR-200b manufactured by Minolta Co., Ltd., and the whiteness is evaluated.
• Titanium manufacturing method is carried out as the final step in the titanium material manufacturing process.
• an ingot process, a hot rolling process, a cold rolling process, an annealing process, and a temper rolling / tensile straightening process are sequentially performed, and then a cleaning process is performed. Will be done.
• the cleaning step is performed after the annealing step when the temper rolling / tensile straightening step is omitted.
• the above steps other than the washing step can be performed by a known method.
• the above-mentioned is carried out by various melting methods such as a vacuum arc melting method, an electron beam melting method or a hearth melting method such as a plasma melting method, using titanium sponge or a mother alloy for adding an alloy element as a raw material.
• a pure titanium or titanium alloy ingot having the above components is prepared.
• the obtained ingot is ingot and hot forged as necessary to form an ingot.
• the ingot may be heated to 600 to 850 ° C. and rolled at a temperature equal to or lower than the transformation point.
• the reduction rate may be determined according to the characteristics of the final product.
• the heating temperature is preferably 700 to 850 ° C.
• the lower limit of the heating temperature is preferably 700 ° C. or higher from the viewpoint of deformation resistance.
• the upper limit of the heating temperature is preferably 850 ° C. or lower because the thickness of the oxide film of the titanium material after hot rolling can be reduced and descaling after hot rolling can be performed under mild conditions. ..
• the titanium material after hot rolling may be rolled under the conditions that the desired thickness and characteristics can be obtained.
• the titanium material may be annealed during the cold rolling passes.
• impurities such as lubricating oil adhering in the cold rolling step may be removed by an alkaline cleaning line, and then this titanium material may be annealed in an inert atmosphere. Further, for example, the titanium material after the cold rolling step may be subjected to atmospheric annealing, salt bath descaling, and pickling in that order.
• the temper rolling / tensile straightening step may be appropriately performed for the purpose of shape straightening of the titanium material after the annealing step, for example.
• zinc salt 0.00030 to 0.65000% by mass in terms of Zn
• calcium salt 0.00060 to 0.40000% by mass in terms of Ca
• HF 1.0 to 6.0% by mass
• zinc salt 0.00030 to 0.00100% by mass in terms of Zn
• calcium salt 0.00060 to 0.00108% by mass in terms of Ca
• HF 1.0 to 6.0% by mass.
• HNO 3 4.0 to 10.0% by mass, soaked in an aqueous solution having a temperature of 40 to 60 ° C. for 1.0 minute or more, and pulled up from the aqueous solution. Includes a water wash treatment to wash the titanium material with water.
• the aqueous solution used in the dipping treatment contains zinc salt in an amount of 0.00030 to 0.65000% by mass in terms of Zn.
• the zinc salt include ZnCl 2 , ZnSO 4 , Zn (NO 3 ) 2 , Zn 3 (PO 4 ) 2 , and ZnCO 3 .
• ZnCl 2 is preferable because it has the highest solubility in water.
• the zinc salt content is 0.00030 to 0.65000% by mass in terms of Zn.
• the content of the zinc salt is less than 0.00030% by mass in terms of Zn, zinc oxide that can suppress the growth of the surface oxide film is not formed on the surface of the titanium material which is the final product. Therefore, the weather resistance becomes poor.
• the upper limit of the zinc salt is 0.65000% by mass or less in terms of Zn.
• the zinc salt content is preferably 0.00150% by mass or less in terms of Zn, but when the zinc salt content is more than 0.00100% by mass in terms of Zn, the weather resistance is good. Zinc oxide formed on the surface oxide film may aggregate.
• the zinc salt content is 0.00100% by mass or less in terms of Zn, color unevenness can be suppressed. Therefore, the zinc salt content is more preferably 0.00100% by mass or less and 0.00080% by mass or less in terms of Zn.
• the zinc salt content is preferably 0.00060 mass% or more in terms of Zn.
• the aqueous solution used in the dipping treatment contains 0.00060 to 0.40000% by mass of calcium salt in terms of Ca.
• the calcium salt include CaCl 2 , CaSO 4 , Ca (NO 3 ) 2 , and CaCO 3 .
• CaCl 2 is preferable because it has high solubility in water and low deliquescent property.
• the content of the calcium salt is 0.00060 to 0.40000% by mass in terms of Ca.
• the content of the calcium salt is less than 0.00060 mass% in terms of Ca, calcium oxide that can suppress the growth of the surface oxide film is not formed on the surface of the titanium material which is the final product. Therefore, the weather resistance becomes poor.
• the upper limit of the calcium salt is 0.40000% by mass or less from the viewpoint of the solubility of the calcium salt and the stable production of the surface oxide film.
• the content of the calcium salt may be 0.00200% by mass or less in terms of Ca. Further, when the content of the calcium salt is more than 0.00108% by mass in terms of Ca, the calcium oxide may aggregate as in the case of the zinc oxide.
• the content of the calcium salt is 0.00108% by mass or less in terms of Ca, color unevenness can be suppressed. Therefore, the content of the calcium salt is preferably 0.00108% by mass or less, and more preferably 0.00100% by mass or less in terms of Ca.
• the calcium salt content is preferably 0.00072% by mass or more in terms of Ca. In the region where the aggregated zinc oxide and calcium oxide are present on the surface of the titanium material, the O concentration is detected to be high by XPS. Therefore, when the zinc oxide and the calcium oxide are aggregated, the value of the thickness of the surface oxide film obtained by the above method becomes large.
• the aqueous solution used in the dipping treatment contains HF: 1.0 to 6.0% by mass and HNO 3 : 4.0 to 10.0% by mass. If the aqueous solution used in the cleaning step contains HF: 1.0 to 6.0% by mass and HNO 3 : 4.0 to 10.0% by mass, fine irregularities are formed on the surface of the titanium material.
• the HF content is 5.0% by mass or less.
• the HNO 3 content is preferably 8.0% by mass or less.
• the HF content is preferably 1.5% by mass or more.
• the HNO 3 content is preferably 4.5% by mass or more.
• the temperature of the aqueous solution is 40 to 60 ° C. If the temperature of the aqueous solution is less than 40 ° C., the titanium material may be pickled unevenly, resulting in uneven color on the surface of the titanium material. On the other hand, if the temperature of the aqueous solution exceeds 60 ° C., a fume of HNO 3 is generated, which adversely affects the manufacturing equipment. Therefore, the temperature of the aqueous solution is 40 to 60 ° C. The temperature of the aqueous solution is preferably 50 ° C. or lower.
• the immersion time is 1.0 minutes or more. If the immersion time is 1.0 minute or more, fine irregularities are formed on the surface of the titanium material without color unevenness.
• the upper limit of the immersion time is not particularly limited, but is preferably 2.0 minutes or less. If the immersion time is 2.0 minutes or less, the treatment can be performed while maintaining the productivity of the continuous line.
• the titanium material is washed with water.
• the washing method is not particularly limited, and the washing may be performed by using a washing bath, spray washing, or the like. By washing with water, an excess aqueous solution on the surface of the titanium material is removed, and a surface oxide film is formed on the surface of the titanium material. At this time, the oxides of Zn 2+ and Ca 2+ adsorbed on the surface of the titanium material are formed.
• the titanium material according to the present embodiment is produced through the cleaning step.
• the titanium material after the cleaning step is used under an inert atmosphere, if necessary. It is preferable to heat to 300 to 900 ° C. By heating the titanium material after the cleaning process to 300 to 900 ° C. in an inert atmosphere, the titanium dioxide ions incorporated in the surface oxide film are decomposed by heating, and F is discharged to the outside of the surface oxide film.
• the inert atmosphere is, for example, a vacuum atmosphere, an argon atmosphere, a helium atmosphere, or the like.
• the vacuum atmosphere referred to here refers to an atmosphere in which the degree of vacuum is 7.0 ⁇ 10 ⁇ 4 to 2.5 ⁇ 10 ⁇ 2 Pa.
• the argon atmosphere means an atmosphere containing 90% by volume or more of argon
• the helium atmosphere means an atmosphere containing 90% by volume or more of helium.
• the heating time is preferably 0.5 to 10.0 (hours). If the heating time is within the above range, the titanate fluoride in the surface oxide film taken in during the dipping treatment is sufficiently decomposed.
• the lower limit of the heating time is more preferably 1.0 hour, and the upper limit of the heating time is more preferably 5.0 hours.
• Table 1 is an example of the quantitative analysis result by XPS on the surface of the titanium material and the example of the quantitative analysis result by XPS on the surface of the general titanium material according to the present embodiment.
• "-" in Table 1 indicates that it was below the detection limit.
• the titanium material according to the present embodiment had a Zn content of 0.3 atomic% and a Ca content of 0.7 atomic%, which were higher than those of the conventional material.
• the method for producing the titanium material according to the present embodiment has been described above.
• Example 1 Titanium cold-rolled plates (titanium base materials) of the varieties shown in Table 2 were produced, and a plurality of samples of various sizes were cut out from the cold-rolled plates and immersed under the conditions shown in Table 2.
• Table 2 shows the dipping treatment conditions. Subsequently, the cold rolled plate after the dipping treatment was washed with water by the following method. That is, the pickling liquid on the surface was removed by immersing the cold rolled plate in a water washing bath at room temperature (25 ° C.) for 1 minute after the dipping treatment. No. in Table 2 No. 1 is an example in which the cleaning step was not carried out (an example in which the cold-rolled annealing remained). No.
• CP1 shown in the item of titanium material varieties in Table 2 indicates industrial pure titanium JIS1 type
• CP2 indicates industrial pure titanium JIS2 type
• CP3 indicates industrial pure titanium JIS3 type.
• the underlined conditions in Table 2 indicate that the conditions are outside the scope of the present invention.
• the analysis conditions by XPS are as follows.
• SiO 2 conversion value is a sputtering speed obtained under the same measurement conditions using a SiO 2 film whose thickness has been measured in advance using an ellipsometer.
• Color difference ⁇ E * ab [( ⁇ L * ) 2 + ( ⁇ a * ) 2 + ( ⁇ b * ) 2 ] 1/2 Asked according to.
• the color difference was measured by using a colorimeter CR-200b manufactured by Minolta Co., Ltd. at the light source C. Specifically, a sample having a maximum value of color difference ⁇ E * ab between each measurement point of 5 or less is judged to have a good evaluation result (OK), and a sample having a maximum value of color difference ⁇ E * ab of more than 5 is judged to be good. It was judged that the evaluation result was defective (NG).
• L * , a * , and b * were measured according to JIS Z8730: 2009, and the whiteness was evaluated by comparing with L * before the washing step.
• the whiteness was measured on the front and back sides at one center and four corners of the sample in the same manner as above, and L * obtained by averaging a total of 10 points was used for the evaluation of whiteness. Since the L * (whiteness) of the sample before the cleaning process was about 65, the evaluation standard was the whiteness to which the difference could be clearly recognized visually compared to the sample before the cleaning process. And said.
• a sample having an L * of 70 or more was judged to have a good evaluation result (OK), and a sample having an L * of less than 70 was judged to have a poor evaluation result (NG).
• the results are shown in Table 3.
• "-" in Table 3 indicates that it was below the detection limit.
• the underlined conditions in the XPS analysis and surface oxide film items in Table 3 indicate that the conditions are outside the scope of the present invention, and the weather resistance, color unevenness, and whiteness in the same table are shown.
• the underlined values in the items indicate the values for which the evaluation result was NG.

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