FAR-INFRARED EMITTER OF HIGH EMISSIVITY AND CORROSION RESISTANCE AND METHOD FOR THE PREPARATION THEREOF

Abstract: A far-infrared emitter of high corrosion resistance is prepared by an oxidizing heat treatment of a body made from a stainless steel of 20-35% by weight of chromium, 0.5-5.0% by weight of molybdenum, up to 3.0% by weight of manganese and up to 3.0% by weight of silicon at 900-1200 °C to form an oxi­ dized surface film having a thickness of at least 0.2 mg/cm². Further, a far-infrared emitter of a high emissivity approximat­ ing a black body is prepared by subjecting a body made from a stainless steel of 10-35% by weight of chromium, 1.0-4.0% by weight of silicon and up to 3.0% by weight of manganese to a blasting treatment to roughen the surface followed by an oxid­ izing heat treatment at 900-1200 °C to form an oxide film on the surface in the form of protrusions having a length of at least 5 µm.

Description: BACKGROUND OF THE INVENTION The present invention relates to a far-infrared emitter of high emissivity and corrosion resistance and a method for the preparation thereof. More particularly, the invention relates to a stainless steel-made far-infrared emitter having a high emissivity approximating that of a black body and excellent corrosion resistance suitable as a heater element in room heaters and drying or heating apparatuses utilizing far-infrared rays as well as a method for the preparation thereof. As is well known, far-infrared rays have a characteristic of easily penetrating human bodies and various kinds of organic materials so that room heaters utilizing far-infrared rays are advantagesous in respect of the high efficiency of heat absorption in the depth of the human body and far-infrared drying or heating ovens can be advantageously used for drying of paint-coated surfaces or heating of various kinds of food by virtue of the rapidness of heating. Several metal oxides such as zirconium oxide, aluminum oxide, silicon dioxide and titanium dioxide are known to emit far-infrared rays with a high efficiency at high temperatures so that many of the far-infrared emitters currently in use are manufactured from a ceramic material mainly composed of one or more of these metal oxides or by providing a metal-made substrate with a ceramic coating layer composed of these metal oxides. Such a ceramic-based far-infrared emitter, however, is practically defective in respect of the fragility to be readily broken by shocks and lack of versatility to the manufacture of large-sized emitters. Metal-based ceramic-coated far-infrared emitters are also not without problems because the ceramic coating layer is liable to fall during use off the substrate surface in addition to the expensiveness of such an emitter. In view of the above mentioned problems in the ceramic-based far-infrared emitters, many proposals have been made for metal-made heat radiators of infrared emitters. For example, Japanese Patent Publication 59-7789 discloses a heat radiator made of an alloy of nickel and chromium, iron and chromium or iron, chromium and nickel provided with a black oxide film on the surface mainly composed of an oxide of chromium formed by the oxidation at a high temperature. Japanese Patent Publication 59-28959 discloses a stainless steel-made infrared heater element provided with an oxide surface film having a thickness of 1 to 10 µm formed by an oxidation treatment at a high temperature of 700 °C or higher. Japanese Patent Publication 60-1914 discloses an infrared-radiating heater element made of a highly heat resistant alloy such as Incoloy (reg. Trade Mark) and subjected to an oxidation treatment at a high temperature of 800 °C or higher. Further, Japanese Patent Kokai 55-6433 discloses a stainless steel-made radiator provided with an oxide surface film formed by a wet process after roughening of the surface to have a surface roughness of 1 to 10 µm. While it is desirable that a far-infrared emitter has an emissivity as high as possible, the above described ceramic-based or stainless steel-based emitters have an emissivity rarely exceeding 0.9 or, in most cases, 0.8 or smaller. Far-infrared emitters usually utilize the far-infrared rays emitted from the emitter body at a temperature in the range from 100 to 500 °C. As is understood from the Planck's law of radiation distribution, an emitter of low emissivity can emit a far-infrared radiation identical with that from an emitter of higher emissivity only when it is heated at a higher temperature. Needless to say, a larger energy cost is required in order to heat an emitter at a higher temperature. Moreover, certain materials are susceptible to degradation when exposed to a radiation of shorter wavelength such as near-infrared and visible rays so that heat radiators used for such a material are required to emit far-infrared rays alone and the far-infrared emitter should be kept at a relatively low working temperature not to emit radiations of shorter wavelengths. Accordingly, it is eagerly desired to develop a far-infrared emitter having a high emissivity even at a relatively low temperature. Apart from the above described problem in the emissivity, stainless steel-made far-infrared emitters in general have another problem of relatively poor corrosion resistance. Namely, the working atmosphere of a far-infrared emitter is sometimes very corrosive. For example, a large volume of water vapor is produced when a water-base paint is dried or food is heat-treated with a far-infrared emitter to form an atmosphere of high temperature and very high humidity. When the working hours of such a heating furnace come to the end of a working day, the furnace is switched off and allowed to cool to room temperature so that the water vapor in the atmosphere is condensed to cause bedewing of the surface of the stainless steel-made far-infrared emitter. Thus, it is usually unavoidable that rusting of the stainless steel-made far-infrared emitter starts within a relatively short time as a consequence of the repeated cycles of heating and bedewing. Once rusting has started, it would be before long that scale of the rust comes off the surface to enter the food under the heat treatment or to adhere to the fabric material under drying so that the heating furnace can no longer be used without entrirely replacing the far-infrared emitter elements in order to obtain acceptable products. SUMMARY OF THE INVENTION The present invention accordingly has an object to provide a novel far-infrared emitter free from the above described problems and disadvantages in the conventional stainless steel-made far-infrared emitters in respect of the emissivity and corrosion resistance as well as an efficient method for the preparation of such a far-infrared emitter. Thus, the far-infrared emitter having, according to the invention, excellent corrosion resistance is a body made from a stainless steel, comprising: from 20 to 35% by weight of chromium; from 0.5 to 5.0% by weight of molybdenum, up to 3.0% by weight of manganese, up to 3.0% by weight of silicon, titanium, niobium or zirconium in an amount up to 0.5% by weight, and a rare earth element such as yttrium, cerium, lanthanum, neodymium and the like in an amount up to 0.3% by weight. the balance being iron and unavoidable impurities, and having an oxidized surface film of a thickness corresponding to at least 0.2 mg/cm². The above defined far-infrared emitter of the invention can be prepared by heating a body made from the above specified stainless steel in an oxidizing atmosphere at a temperature in the range from 900 °C to 1200 °C for a length of time which is at least 5 minutes when the heating temperature is 1100 °C or higher and at least (142.5 - 0.125T) minutes when the heating temperature is lower than 1100 °C, T being the heating temperature given in °C. BRIEF DESCRIPTION OF THE DRAWING Figure 1 is an electron microphotograph of the surface of a high-emissivity far-infrared emitter according to the invention. Figure 2 is a similar electron microphotograph of a conventional stainless steel-made far-infrared emitter. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The corrosion-resistant far-infrared emitter according to the present invention is made from a stainless steel based on iron, chromium and molybdenum as the essential alloying elements together with the optional additive elements of claim 1 each in a specified proportion. Such a composition of stainless steels is not novel. The amount of and the role played by each of the alloying elements in the stainless steel are as follows. Firstly, silicon in the stainless steel has an effect to increase the oxidation resistance of the stainless steel so as to facilitate the oxidation treatment thereof at a high temperature. However, a too large amount of silicon in the stainless steel is detrimental in respect of the decreased ductility of the material not only in the base metal but also in the welded portion. This is the reason that the amount of silicon in the stainless steel should not exceed 3.0% by weight. Secondly, addition of manganese to the stainless steel has an effect to decrease the strength of the material not only in the base metal but also in the welded portion along with an adverse effect on the oxidation resistance of the stainless steel at high temperatures. Accordingly, the amount of manganese in the stainless steel should not exceed 3.0% by weight. Thirdly, chromium is one of the essential elements in stainless steels in order that the stainless steel may have corrosion resistance. When the amount of chromium is smaller than 20% by weight, no satisfactory corrosion resistance can be imparted to the stainless steel. When the amount of chromium exceeds 35% by weight, on the other hand, the steel may have brittleness to cause difficulty in fabrication into an emitter body. This is the reason for the limitation in the amount of chromium in the range from 20 to 35% by weight. Fourthly, molybdenum is another essential element in the stainless steel for shaping the far-infrared emitter of the invention and has an effect to improve the corrosion resistance of the stainless steel after an oxidation treatment at high temperatures. When the amount of molybdenum is smaller than 0.5% by weight, the above mentioned advantageous effect cannot be fully obtained. When the amount of molybdenum exceeds 5.0% by weight, on the other hand, the steel may have brittleness so that the steel cannot be worked into a thin plate or sheet. This is the reason for the limitation in the amount of molybdenum in the range from 0.5% to 5.0% by weight. In addition to the above mentioned elements including chromium, molybdenum, silicon and manganese, various kinds of additive elements can be added to the stainless steel according to the established formulation of stainless steels. For example, addition of titanium, niobium or zirconium in an amount up to 0.5% by weight is effective in improving the strength and oxidation resistance of the stainless steel in the base metal as well as in the welded portions. Further, addition of a rare earth element such as yttrium, cerium, lanthanum, neodymium and the like in an amount up to 0.3% by weight is effective in preventing falling of the oxidized surface film off the surface of the emitter body. Addition of these auxiliary elements is of course optional in the chromium-molybdenum-based stainless steel used for shaping the far-infrared emitter of the invention. The above defined stainless steel is fabricated into a thin plate which is subjected to a heat treatment in an oxidizing atmosphere to be provided with an oxidized surface film. The temperature of the heat treatment is in the range from 900 °C to 1200 °C. When the temperature is lower than 900 °C, the diffusion velocity of chromium in the steel is low from the core portion to the surface layer not to fully compensate the amount of chromium lost in the form of an oxide out of the surface so that a chromium-deficient layer having a thickness of up to several tens of micrometers is formed on the surface with consequently decreased corrosion resistance of the emitter. Such a chromium-deficient layer is not formed on the surface when the heat treatment is performed at a temperature of 900 °C or higher as a result of the increased diffusion velocity of chromium to impart the plate with high corrosion resistance. When the temperature of the heat treatment exceeds 1200 °C, however, high-temperature distortion takes place in the stainless steel plate so remarkably that the plate can no longer be used as a material of the far-infrared emitter of the invention. It is essential that the oxidized surface film formed by the heat treatment of the stainless steel plate in an oxidizing atmosphere has a thickness corresponding to a weight of at least 0.20 mg/cm² in order that the emitter may have a satisfactory emissivity of far-infrared rays. Such a thickness of the oxidized surface film can be obtained by conducting the oxidizing heat treatment for a sufficient length of time. When the temperature of the heat treatment is in the range from 900 °C to 1100 °C, the length of time for the treatment must be at least (142.5 - 0.125T) minutes, T being the temperature in °C, and, when the temperature is in the range from 1100 °C to 1200 °C, the heat treatment must be continued for at least 5 minutes. The oxidizing atmosphere used in the oxidizing heat treatment is not limited to the atmospheric air as such but can be an oxygen-enriched gaseous mixture of oxygen and a non-oxidizng gas such as nitrogen, argon, helium and the like together with or without water vapor. Various kinds of combustion gases are also used satisfactorily for the oxidizing atmospheric gas in the inventive method. The oxidized surface film should have a thickness corresponding to a weight of at least 0.2 mg/cm² or, preferably, in the range from 0.2 mg/cm² to 10 mg/cm² or, more preferably, in the range from 0.5 mg/cm² to 2.0 mg/cm². When the thickness is too large, the oxidized surface film may readily fall off the surface of the substrate as a trend. It is sometimes effective to increase the surface roughness of the stainless steel plate in order to have an increased effective surface area for emission of far-infrared rays. For example, satisfactory results may be obtained with a stainless steel plate after a blasting treatment or dull rolling. In the following, examples are given to illustrate the inventive far-infrared emitters in more detail. Example 1. Eight kinds of steels A to H were used in the tests each in the form of a plate having a thickness of 1.0 mm after annealing and acid washing including six commercially available steels A, B, D, E, F and G and two laboratory-made steels C and H prepared by melting, casting and rolling. Table 1 below shows the grade names and chemical compositions of these steels. Each of these stainless steel plates was cut by shearing into 10 cm by 10 cm square plates, referred to as the samples No. 1 to No. 12 hereinbelow, which were subjected to a surface treatment I, II or III specified below excepting for the samples No. 2, No. 5 and No. 12 followed by a high-temperature oxidizing treatment in air under the conditions shown in Table 2. Surface treatment I : sand blasting with #180 SiC abrasive powder II : shot blasting with steel balls of 0.1 mm diameter III : dull rolling, i.e. rolling with a surface-roughened roller Steel No. C Si Mn Cr Mo Ni Others A 30Cr2Mo 0.003 0.2 0.1 30.1 1.9 <0.1 Nb 0.14 B 26Cr4Mo 0.003 0.2 0.1 26.2 3.7 <0.1 Nb 0.16 C 30Cr1Mo 0.005 0.4 0.2 29.2 0.9 <0.1 Ti 0.1 REM 0.1 D 18Cr2Mo 0.004 0.1 0.3 17.8 1.8 0.3 Nb 0.3 E SUS 430 0.04 0.4 0.4 17.4 <0.1 0.2 Ti 0.2 F SUS 304 0.06 0.5 1.5 18.5 <0.1 8.2 G Incoloy 0.024 0.4 0.4 20.4 <0.1 31.1 Ti 0.3 Al 0.3 H 25Cr 0.011 0.4 0.2 24.8 <0.1 <0.1 The stainless steel test plates after the high-temperature oxidation treatment were subjected to the measurement of the center-line average height of surface roughness R a defined in JIS B 0601 by using a tracer-method surface roughness tester specified in JIS B 0651. The test plates were accurately weighed before and after the high-temperature oxidation treatment to determine the increment in the weight by the oxidation treatment per unit surface area. The amount of oxidation in mg/cm² shown in Table 2 is the thus obtained value after multiplication by a factor of 3.3. This is because an X-ray analysis of the oxide film on each of the test plates indicated that the oxide film had a chemical composition approximately corresponding to Cr₂O₃ to give a weight ratio of Cr₂O₃ to oxygen equal to 3.3. In the next place, the infrared emissivity of each of the test plates was obtained as an average ratio of the intensity of infrared emission at 400 °C in the wavelength region of 5 to 15 µm to the black body emission at the same temperature in the same wavelength region. The results are shown in Table 2. The results in Table 2 indicate the criticality of the oxidation temperature and the length of the oxidation treatment. Thus, the sample No. 6, oxidized for 12 hours at a low temperature of 850 °C, and sample No. 7, oxidized at 1000 °C for a short time of 10 minutes, each had an amount of oxidation of only 0.1 mg/cm² to give an emissivity of 0.5 which should be compared with the emissivity of 0.8 and 0.7 obtained in the samples No. 1 and No. 2 prepared from the same kind of the stainless steel A. A practically acceptable emissivity of 0.7 or higher could be obtained in all of the test plates excepting No. 6 and No. 7. In this regard, dull rolling for the surface treatment was effective to give an emissivity of 0.8 or higher on the test plates having the thus roughened surface. In particular, an improvement in the productivity of the oxidation treatment was obtained by using the steel C as is shown by the sample No. 5 which could be fully oxidized at a high temperature of 1200 °C within a short time of 0.5 hour by virtue of the addition of 0.1% by weight of rare earth elements, i.e. mixture of cerium, lanthanum and neodymium, to the 30Cr1Mo steel with an object to prevent falling of the oxide film from the surface. Finally, the salt spray test specified in JIS Z 2371 was undertaken for 4 hours to determine the corrosion resistance of the test plates to give the results shown in Table 2. As is shown there, no rusting at all was found on each of the test plates No. 1 to No. 5 according to the invention while rusting was found in part on the sample No. 6, prepared from the 30Cr2Mo steel but oxidized at a low temperature of 850 °C, sample No. 8, prepared from the 18Cr2Mo steel of low chromium content of 18% by weight, and sample No. 11, prepared from Incoloy, and rusting was found allover the surface on the samples No. 9, No. 10 and No. 12 prepared from SUS 430, SUS 304 and 25Cr steel, respectively. Example 2. Stainless steel plates having a thickness of 1.0 mm were prepared by rolling two different chromium-silicon steels I and J having a chemical connosition shown in Table 3 followed by annealing and acid washing. Test plates of infrared emitters were prepared from these laboratory-made stainless steel plates I and J as well as from commercially available plates of stainless steels SUS 430 and SUS 304 (steels E and F, see Table 1) having a thickness of 1.0 mm for comparative purpose. Steel No. C Si Mn Cr Ni Others I 11Cr1.5Si 0.01 1.5 0.2 11.2 0.2 Ti 0.2 J 25Cr3Si 0.005 2.9 2.1 25.1 <0.1 Ti 0.2 REM 0.1 Each of the stainless steel plates I, J, E and F was cut into 10 cm by 10 cm squares which were subjected first to a blasting treatment and then to a high-temperature oxidation treatment in air under the conditions shown in Table 4 given below. The conditions of the blasting treatments I and II shown in the table were the same as in Example 1. Each of the test plates after the blasting treatment excepting the sample No. 16 was subjected to the measurement of the surface roughness in the same manner as in Example 1 to find a substantial increase in the surface roughness from about 0.3 µm on the plates of the steels I and J and about 0.2 µm on the plates of the steels E and F to about 1.8 to 2.9 µm on the plates after the shot blasting treatment with steel balls and about 0.8 to 1.4 µm on the plates after the blasting treatment with the silicon carbide abrasive powder. The surface condition of these test plates after the oxidation treatment was examined using an electron microscope to give the photographs of Figures 1 and 2 indicating the surface condition of the sample No. 13 according to the invention and the sample No. 16 for comparative purpose, respectively. Further, microphotographs of 800 magnifications were taken of the surface of the test plates inclined at an angle of 60° to estimate the length of the oxide protrusions, of which an average of the actual values was calculated and shown in Table 4. As is shown in the table, no protrusions of the oxide film were found on the sample No. 16 prepared by omitting the blasting treatment and the samples No. 18 and No. 19 prepared from the stainless steels SUS 430 and SUS 304, respectively, containing no silicon. The length of the oxide protrusions was about 3 µm on the sample No. 17 prepared by the high-temperature oxidation treatment for a relatively short time of 30 minutes. The samples No. 13 to No. 15 each had oxide protrusions of a length of at least 7 µm. The test plates were subjected to the measurement of the emissivity in the wavelength region of 5 to 15 µm in the same manner as in Example 1 to give the results shown in Table 4. The emissivity was 0.7 to 0.9 on the samples No. 17 to No. 19 having no protrusions of the oxide film and on the sample No. 16 of which the length of the oxide protrusions was only about 3 µm while the samples No. 13 to No. 15 had a quite high emissivity of 1.0 to approximate a black body.

Claims: A far-infrared emitter having high corrosion resistance which is a body made from a stainless steel comprising from 20 to 35% by weight of chromium; from 0.5 to 5.0% by weight of molybdenum; up to 3.0% by weight of manganese and up to 3.0% by weight of silicon, titanium, niobium or zirconium in an amount up to 0.5% by weight and a rare earth element such as yttrium, cerium, lanthanum, neodymium and the like in an amount up to 0.3% by weight, the balance being iron and unavoidable impurities, and having an oxidized surface film with a thickness corresponding to a weight of at least 0.2 mg/cm². A method for the preparation of a far-infrared emitter having high corrosion resistance which comprises the step of heating, in an oxidizing atmosphere, a body made from a stainless steel comprising from 20 to 35% by weight of chromium, from 0.5 to 5.0% by weight of molybdenum, up to 3.0% by weight of manganese and up to 3.0% by weight of silicon, titanium, niobium or zirconium in an amount up to 0.5% by weight and a rare earth element such as yttrium, cerium, lathanum, neodymium and the like in an amount up to 0.3% by weight, the balance being iron and unavoidable impurities, at a temperature in the range from 900° C to 1200° C for a length of time which is at least 5 minutes when the heating temperature is 1100° C or higher and at least (142.5 - 0.125T) minutes when the heating temperature is lower than 1100° C, T being the heating temperature given in °C, so as to form an oxide film on the surface of the body having a thickness corresponding to a weight of at least 0.2 mg/cm². The far-infrared emitter having high corrosion resistance as claimed in claim 1 wherein the oxidized surface film has a thickness corresponding to a weight in the range from 0.5 to 2.0 mg/cm². The method for the preparation of a far-infrared emitter as claimed in claim 2 wherein the oxidizing atomsphere is atmospheric air.

Inventors: DOHI, SHOJI, ISHII, KAZUHIDE C/O RESEARCH LABORATORIES OF, KAWASAKI, TATSUO C/O RESEARCH LABORATORIES OF, KURIYAMA, NORIYUKI C/O HANSHIN WORKS OF KAWASAKI, MIYAZAKI, SOUHEI, NAKASHIBA, AKIO
Applicants: KAWASAKI STEEL CORPORATION, OSAKA GAS CO., LTD
Application year: 1989
Main classification: C22C38
IPC codes: H05B3, C22C38, C23C8