US20050028903A1 - High aluminiferous ferritic stainless steel sheet for weight sensor substrate, method for producing the same, and weight sensor - Google Patents

High aluminiferous ferritic stainless steel sheet for weight sensor substrate, method for producing the same, and weight sensor Download PDF

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US20050028903A1
US20050028903A1 US10/928,551 US92855104A US2005028903A1 US 20050028903 A1 US20050028903 A1 US 20050028903A1 US 92855104 A US92855104 A US 92855104A US 2005028903 A1 US2005028903 A1 US 2005028903A1
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stainless steel
steel sheet
weight sensor
aluminiferous
ferritic stainless
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Masuhiro Fukaya
Tadashi Komori
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Nippon Steel Stainless Steel Corp
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Publication of US20050028903A1 publication Critical patent/US20050028903A1/en
Priority to US12/152,505 priority Critical patent/US8500923B2/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

Definitions

  • the present invention relates to a high aluminiferous ferritic stainless steel sheet for the weight sensor substrate of an automobile airbag, a method for producing the ferritic stainless steel sheet, and a weight sensor.
  • An automobile is equipped with seatbelts and airbags as devices for securing the safety of occupants.
  • seatbelts and airbags as devices for securing the safety of occupants.
  • body weight an occupant's weight
  • the expansion gas volume and expansion speed of an airbag and the pretensioning of a seatbelt are adjusted in conformity with an occupant's weight.
  • a mechanical quantity sensor for detecting load, pressure, etc. various sensors has been proposed in accordance with the kind of a substrate and the kind of a strain sensitive material used for a resistive element.
  • Typical proposed examples are: (1) a sensor produced by using a film comprising a resin such as polyester, epoxy, polyimide or the like as a substrate and forming on the surface of the substrate a lamellar resistive element comprising Cu—Ni alloy, Ni—Cr alloy or the like by vapor deposition or sputtering, (2) a sensor produced by using a glass plate instead of the aforementioned resin film (Japanese Examined Patent Publication No.
  • the magnitude of a mechanical quantity is measured in the following way.
  • a force or a load is imposed on a mechanical quantity sensor from outside, a resistive element formed on the surface of a substrate deforms together with the substrate.
  • the imposed mechanical quantity is detected by measuring the change of an electric resistance between a pair of electrodes formed by connecting the resistive element, the change of the electric resistance being caused by the change of the length and sectional area of the resistive element.
  • a mechanical quantity sensor that uses a metal base material on the surface of which a crystallized glass layer is formed as a substrate is most suitable as a sensor used under a harsh environment because, unlike other types of sensors, each of the component elements interdiffuses between the metal base material and the crystallized glass layer and also between the crystallized glass layer and a resistive element, and thus the adhesiveness between them is very strong.
  • a resistive element of a mechanical quantity sensor of this type an element formed by being coated with resistive paste containing ruthenium oxide that functions as a resistive material, then dried and baked is known.
  • Japanese Unexamined Patent Publication No. 2000-180255 discloses a technology that uses a stainless steel sheet as a metal base material.
  • Japanese Unexamined Patent Publication No. H10-38733 discloses a technology that uses SUS 430 as a metal base material from the viewpoint of the adhesiveness with an insulating glass layer.
  • Japanese Unexamined Patent Publication No. H5-93659 discloses a technology that uses SUS 430 concretely as a metal base material from the viewpoint of the necessity of coordinating the expansion coefficient thereof with that of a glass layer.
  • a sensor substrate is made of a stainless steel sheet and that an insulating glass layer and the layers of a resistive element and electrodes are solidified by baking (the schematic illustration is shown in FIG. 1 ).
  • a stainless steel that has a high thermal resistance and an excellent glass adhesiveness so that sensor members may be baked together when each of the layers is baked at a high temperature has strongly been longed for.
  • the adhesiveness between them deteriorates considerably and therefore they do not function as the substrate of a resistive element.
  • the average linear expansion coefficient of generally used crystallized glass is 13 to 16 ⁇ 10 ⁇ 6 /° C.
  • that of a conventionally used stainless steel is about 13 ⁇ 10 ⁇ 6 /° C. Accordingly, the difference in the average linear expansion coefficient is too large between the stainless steel substrate and the glass layer, and thus sufficient glass adhesiveness cannot be obtained.
  • the object of the present invention is, by providing a stainless steel most suitable as a metal base material for the weight sensor substrate of an automobile airbag, to improve high temperature oxidation resistance when the stainless steel substrate is sintered with a crystallized glass layer and thus to enhance the adhesiveness thereof with the glass layer.
  • the present invention has been established as a result of studying components, production methods, linear expansion coefficients and high temperature oxidation resistance in order to attain the above object, and it has been found that the object can be achieved by applying to a metal base material a steel sheet produced containing Nb, preferably further V, Ti and Zr, in a high aluminiferous ferritic stainless steel sheet.
  • the gist of the present invention is as follows.
  • the object of the present invention is attained by a high aluminiferous ferritic stainless steel sheet and a method for producing the stainless steel sheet according to the following points (1) to (7).
  • a high aluminiferous ferritic stainless steel sheet for a weight sensor substrate characterized by comprising a high aluminiferous ferritic stainless steel containing, in mass,
  • a high aluminiferous ferritic stainless steel sheet for a weight sensor substrate according to the item (1) characterized in that said high aluminiferous ferritic stainless steel further contains, in mass, one or more of
  • a method for producing a high aluminiferous ferritic stainless steel sheet for a weight sensor substrate characterized by stamping said high aluminiferous ferritic stainless steel sheet according to the item (1) or (2) into a desired shape and successively applying heat treatment for 20 to 120 minutes in the temperature range from 800° C. to 900° C.
  • a weight sensor characterized by being composed of: a weight sensor substrate comprising said high aluminiferous ferritic stainless steel sheet according to the item (1) or (2); a crystallized glass layer with which the surface of said substrate is covered; strain sensitive resistive elements formed on the surface of said crystallized glass layer; and a pair of electrodes for detecting the change of the electric resistance of said strain sensitive resistive elements.
  • the high aluminiferous ferritic stainless steel sheet of the present invention is a substrate material excellent in glass adhesiveness and high temperature oxidation resistance and is inevitable technology for sensor substrate material with which an insulating layer is adhered.
  • FIG. 1 is a schematic illustration showing a mechanical quantity sensor according to the present invention.
  • FIG. 2 is a graph showing the distribution of average linear expansion coefficients in the range from the room temperature (20° C.) to 900° C. in relation to the contents of Cr and Al of the stainless steel.
  • FIG. 3 is a graph showing the relationship between an Al content and an average linear expansion coefficient of the stainless steel in the range from the room temperature (20° C.) to 900° C.
  • the present invention has been established as a result of studying the components of stainless steels, production methods, linear expansion coefficients and high temperature oxidation resistance, and provides a material excellent in glass adhesiveness used for a weight sensor substrate of an automobile airbag by adopting as the metal base material a stainless steel sheet produced containing Nb in a high aluminiferous ferritic stainless steel sheet and preferably further containing V, Ti and Zr therein.
  • Cr is the most fundamental element in securing the thermal resistance or high temperature oxidation resistance of a stainless steel.
  • a Cr content is less than 12 mass %, such properties are secured insufficiently and in contrast, when Cr is contained in excess of 30 mass %, particularly the toughness and ductility of a hot-rolled steel strip deteriorate considerably and the producibility of the material also deteriorates.
  • a Cr content is limited in the range from 12 to 30 mass %, preferably from 14.5 to 16 mass %.
  • Al is an element that remarkably improves the high temperature oxidation resistance and specific resistance of a ferritic stainless steel.
  • a linear expansion coefficient increases. Therefore, in the present invention, it is possible to make the linear expansion coefficient of a ferritic stainless steel coordinate with and approximate various linear expansion coefficients of various crystallized glass layers by alloy design wherein mainly an Al mass % is adjusted.
  • FIG. 2 shows the distribution of average linear expansion coefficients in the range from room temperature (20° C.) to 900° C. in relation to the contents of Cr and Al of the stainless steel. It is understood that an average linear expansion coefficient depends not on a Cr content but on an Al content.
  • FIG. 3 shows the relationship between an Al content and an average linear expansion coefficient of the stainless steel.
  • the approximate expression of an average linear expansion coefficient a in the range from the room temperature (20° C.) to 900° C. is 12.8+0.28 ⁇ (Al mass %) when an Al content is about 8 to 9 mass % or lower, and 2.9+1.4 ⁇ (Al mass %) when an Al content exceeds about 9 mass %.
  • the average linear expansion coefficient of generally used crystallized glass is 13 to 16 ⁇ 10 ⁇ 6 /° C., and therefore it becomes possible to control the difference in the linear expansion coefficient between a stainless steel substrate and employed crystallized glass within an allowable range by adjusting an Al content in the range of 8 mass % or less.
  • an Al content is limited in the range from 2.5 to 8 mass %, preferably 4 to 6 mass %.
  • a stainless steel sheet according to the present invention is a high aluminiferous stainless steel sheet and the toughness thereof lowers after hot rolling. Therefore, it is necessary to secure toughness in order to improve workability.
  • the present invention is aimed at securing the toughness of a steel sheet by regulating components as follows.
  • C and N when they are contained in excess of 0.025 mass % respectively, deteriorate the toughness of a hot-rolled steel strip which is the raw material of a cold-rolled steel sheet and the producibility of the material, namely cold-rolling operability. Therefore, the contents of C and N are limited to 0.025 mass % or less respectively and the sum of C and N is limited to 0.030 mass % or less. Preferably, the contents of C and N are 0.010 mass % or less respectively and the sum of C and N is also 0.010 mass % or less.
  • Nb is an element that forms carbonitride, thus prevents Cr carbide from precipitating at grain boundaries, refines crystal grains, enhances the toughness of a hot-rolled steel strip, and thus improves the producibility of the material. Therefore, it is possible to enhance the toughness of a hot-rolled steel strip by containing Nb in a stainless steel according to the present invention.
  • Nb content is less than 0.05 mass %, the effect is insufficient.
  • Nb content exceeds 0.5 mass %, workability deteriorates considerably at cold rolling.
  • a Nb content is limited in the range from 0.05 to 0.5 mass %, preferably 0.1 to 0.3 mass %.
  • V can be added selectively in the present invention. V further enhances the toughness of a hot-rolled steel strip by the same effect as Nb. When a V content is less than 0.05 mass %, the effect is insufficient. In contrast, when a V content exceeds 0.4 mass %, workability deteriorates considerably at cold rolling. For those reasons, a V content is limited in the range from 0.05 to 0.4 mass %.
  • Ti can be added selectively in the present invention.
  • Ti is an element that is effective in improving the high temperature oxidation resistance of a ferritic stainless steel and improves the adhesiveness of an oxide film. With a Ti content of 0.02 mass % or more, the effect can show up. However, an excessive addition of Ti deteriorates the toughness of a hot-rolled steel strip and also the producibility of the material. When a Ti content exceeds 0.2 mass % in particular, the deterioration of toughness is conspicuous. For these reasons, a Ti content is limited in the range from 0.02 to 0.2 mass %, preferably from 0.04 to 0.10 mass %.
  • Zr can be added selectively in the present invention.
  • Zr exhibits the same effect as Ti does and is an element that is effective in improving the high temperature oxidation resistance of a ferritic stainless steel and improves the adhesiveness of an oxide film. With the addition of Zr by 0.02 mass % or more, the effect can be exhibited. In contrast, an excessive addition of Zr deteriorates not only oxidation resistance but also the toughness of a hot-rolled steel strip and thus the producibility of the material. When a Zr content exceeds 0.2 mass % in particular, the deterioration of toughness is conspicuous. For these reasons, a Zr content is limited in the range from 0.02 to 0.2 mass %, preferably 0.05 to 0.15 mass %.
  • a preferable method for hot rolling a high aluminiferous ferritic stainless steel sheet of low carbon and low nitrogen, to which Nb or Nb, V, Ti, and Zr are added in appropriate amounts according to the present invention, is described. Toughness can be enhanced remarkably by: finishing hot rolling a stainless steel slab containing components stipulated in the present invention in the recovery temperature range from 700° C. to the recrystallization temperature; controlling the sum of the reduction ratios in the recovery temperature range not exceeding a recrystallization temperature to 15% or higher; successively coiling the hot-rolled steel strip in the temperature range from higher than 500° C. to lower than 850° C.; and thereafter cooling it mandatorily.
  • the difference in the average linear expansion coefficient between a high aluminiferous ferritic stainless steel sheet and crystallized glass for a weight sensor substrate is less than 10% in the temperature range from 20° C. to 900° C.
  • a crystallized glass layer functioning as an insulating layer a strain sensitive resistive element and electrodes are baked and resultantly solidified in the form of layers onto a stainless steel sheet functioning as the substrate of a sensor, it is necessary to coordinate their linear expansion coefficients with each other in order to improve the adhesiveness between the metal base material and the glass layer. Baking is applied at 900° C.
  • the linear expansion coefficients are close to each other not only in the vicinity of the room temperature but also in the temperature range from 20° C. to 900° C.
  • the difference in the average linear expansion coefficient is more than 10%, the adhesiveness between a metal base material and a crystallized glass layer deteriorates considerably and therefore they do not function as the base of a resistive element.
  • the average linear expansion coefficient of generally used crystallized glass is 13 to 16 ⁇ 10 ⁇ 6 /° C.
  • an appropriate average linear expansion coefficient of a high aluminiferous ferritic stainless steel sheet is 13.5 to 15.5 ⁇ 10 ⁇ 6 /° C. in the temperature range from 20° C. to 900° C.
  • L 20 is a length at 20° C.
  • L T is a length at a temperature T.
  • a high aluminiferous ferritic stainless steel sheet according to the present invention is a cold-rolled annealed steel sheet produced by descaling and thereafter cold rolling a hot-rolled steel strip and successively applying annealing and descaling.
  • a cold-rolled steel sheet of a high aluminiferous ferritic stainless steel sheet according to the present invention is stamped into a desired shape and thereafter baked together with a glass layer.
  • the baking is applied for 20 to 120 minutes at 800° C. to 900° C.
  • a baking temperature is lower than 800° C.
  • the interdiffusion between a stainless steel sheet and a glass layer is insufficient and therefore the adhesiveness is also insufficient.
  • a baking temperature exceeds 900° C., the thermal resistance of a glass layer cannot withstand the temperature.
  • a baking time here is defined by the total hours spent in plural heat treatments. When a baking time is shorter than 20 minutes, interdiffusion is insufficient and thus adhesiveness is also insufficient.
  • temper color an oxide film having the thickness of submicron order is formed due to the progress of oxidation, resulting in discoloration, so-called temper color, and the deterioration of resistance against temper color.
  • the temper color does not directly affect the functions as a sensor but a color tone intrinsic to a stainless steel surface is lost.
  • the thickness of an oxide film formed on the surface of a stainless steel sheet in the baking treatment that is applied to the stainless steel sheet as well as a crystallized glass layer is less than 0.38 ⁇ m.
  • an oxide film thickness is 0.38 ⁇ m or more, it corresponds to the wavelength of visible light (0.38 to 0.78 ⁇ m) and therefore an interference color such as blue-green appears.
  • an oxide film thickness is less than 0.38 ⁇ m, such an interference color does not form and excellent temper color resistance is obtained.
  • An automobile airbag weight sensor is, as shown in FIG. 1 , a weight sensor characterized by being composed of: a substrate 1 comprising a metal base material of a high aluminiferous ferritic stainless steel sheet; a crystallized glass layer 2 with which the surface of the substrate is covered; strain sensitive resistive elements 4 formed on the surface of the crystallized glass layer; and a pair of electrodes 3 for detecting the change of the electric resistance of the strain sensitive resistive elements. Note that, in the weight sensor, volt holes 5 used for putting the weight sensor in place are provided.
  • High aluminiferous ferritic stainless steels shown in Table 1 were melted and refined by the converter AOD method or the vacuum melting method. These steels were subjected to surface conditioning, thereafter hot rolled at a hot-rolling finishing temperature in the range from 880° C. to 900° C., coiled at a hot-rolling coiling temperature in the range from 400° C. to 750° C., and cooled by water cooling, and thus hot-rolled steel strips 5 mm and 3.8 mm in thickness were produced. Successively, the hot-rolled steel strips were subjected to shot blasting and descaling by pickling, and thereafter cold rolled to the thickness of 3 mm and 2 mm. Successively, the cold-rolled steel strips were annealed at 920° C. and then subjected to salt treatment and descaling by pickling, and thus cold-rolled steel sheets were produced. With regard to crystallized glass, crystallized glass having the average linear expansion coefficient of 14.5 ⁇ 10 ⁇ 6 /° C. was used.
  • C, S and N were measured by the gas analysis method (the method of melt in inert gas and thermal conduction measurement in the case of N, and the method of combustion in oxygen stream and infrared-absorbing analysis in the case of C and S), and the other elements were measured with a fluorescent X-ray analyzer (SHIMAZU, MXF-2100).
  • the producibility was evaluated by sampling a V-notched Charpy test piece of sub-size (5 mm or 3.8 mm in thickness) conforming to the JIS Standard in the direction parallel to the rolling direction, subjecting the test piece to an impact test, and measuring the temperature at which the impact value was 2 kgf/cm 2 (vT2:° C.).
  • vT2 kgf/cm 2
  • the high temperature oxidation resistance was evaluated by using a sample the surface of which was polished to #400 in mesh and measuring the increment of oxidation amount after the heating for 120 minutes at 900° C. in the atmosphere.
  • the Cr content was lower than the lower limit stipulated in the present invention in the case of the comparative example No. 13 (sample No. 13) and the Al content was lower than the lower limit stipulated in the present invention in the case of the comparative example No. 15 (sample No. 15), and resultantly the oxidation resistance was inferior in either case of the comparative examples.
  • the linear expansion coefficient was evaluated by adopting the test method stipulated in the ISO Standard and measuring an average linear expansion coefficient in the range from the room temperature (20° C.) to 900° C.
  • the difference in the average linear expansion coefficient between a high aluminiferous ferritic stainless steel sheet and crystallized glass for a weight sensor substrate was within 10% in the temperature range from 20° C. to 900° C.
  • the Al content was lower than the lower limit stipulated in the present invention and also the average linear expansion coefficient in the range from the room temperature to 900° C. was lower than the lower limit stipulated in the present invention.
  • the glass adhesiveness was evaluated by the tape peeling test JIS H8504 (a method for testing the adhesiveness of plating). A case where a crystallized glass layer exfoliated was indicated as X and a case where it did not exfoliate was indicated as ⁇ .
  • the glass adhesiveness of the metal base materials containing the components stipulated in the present invention improved considerably. In the case of the comparative example No. 15, the Al content was lower than the lower limit stipulated in the present invention and resultantly the glass adhesiveness was poor. TABLE 1 Clas- Sam- sifi- ple Chemical components (mass %) cation No. No.
  • the steel sheets of sample Nos. 7 and 3 shown in Table 1 were subjected to baking heat treatment under the conditions shown in Table 2.
  • a coating film thickness was measured by GDS (Glow Discharge Emission Spectrometry).
  • the measuring device was JY500ORF-PSS type made by JOBIN YVON (France) and the measurement area was 4 mm in diameter.
  • a sputter speed was measured by the depth formed after subjecting a Japanese Iron and Steel Certified Reference Material JSS652-13 to the discharge for 250 seconds.
  • As the samples for calibration four kinds of specimens including Japanese Iron and Steel Certified Reference Materials JSS652-13, JSS171-1, JSS1001-1 and the like were used.
  • the resistance to temper color was judged by visually observing the existence of color development at visible wavelengths.
  • the invention example Nos. 7 and 19 to 21 were the cases where the baking conditions stipulated in the present invention were adopted and were excellent in both the glass adhesiveness and temper color resistance.
  • the baking temperature was higher than the upper limit and thus all the glass adhesiveness, film thickness and temper color resistance were inferior.
  • the baking time was longer than the upper limit and thus both the film thickness and temper color resistance were inferior.
  • the baking time was shorter than the lower limit and thus the glass adhesiveness was poor.
  • the baking temperature was lower than the lower limit and thus the glass adhesiveness was poor.

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Publication number Priority date Publication date Assignee Title
EP3604596A4 (en) * 2017-03-30 2020-07-29 Nippon Steel Stainless Steel Corporation FERRITE-BASED STAINLESS STEEL SHEET WITH LOW SPECIFIC WEIGHT AND MANUFACTURING METHOD THEREFOR
US11242578B2 (en) 2017-03-30 2022-02-08 Nippon Steel Stainless Steel Corporation Ferrite-based stainless steel sheet having low specific gravity and production method therefor

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JP3958280B2 (ja) 2007-08-15
US20080245162A1 (en) 2008-10-09
US8500923B2 (en) 2013-08-06

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