JP2014237868A - Carburization method and carburizing treatment gas used for the method - Google Patents

Carburization method and carburizing treatment gas used for the method Download PDF

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JP2014237868A
JP2014237868A JP2013120086A JP2013120086A JP2014237868A JP 2014237868 A JP2014237868 A JP 2014237868A JP 2013120086 A JP2013120086 A JP 2013120086A JP 2013120086 A JP2013120086 A JP 2013120086A JP 2014237868 A JP2014237868 A JP 2014237868A
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JP6234711B2 (en
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吉野　明
Akira Yoshino
明 吉野
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Air Water Inc
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Abstract

PROBLEM TO BE SOLVED: To provide a carburization method which can increase carburization speed, and carburization treatment gas used for the method.SOLUTION: A gas production apparatus for carburizing treatment gas includes: a first heater 1 for heating natural gas; a second heater 3 for heating oxygen gas; a reformer 4 which reforms the natural gas and the oxygen gas passing through the first heater and the second heater by further mixing them, and generates carbon monoxide gas and hydrogen gas; and a pressure swing adsorption apparatus 9 which condenses the carbon monoxide gas and the hydrogen gas obtained by the reformer 4. With the gas production apparatus, the carburizing treatment gas is obtained, which includes hydrogen gas and carbon monoxide gas in the range of 30-60 mol%, and a steel member is carburized using the gas.

Description

本発明は、鋼製部材に対する浸炭方法およびそれに用いる浸炭処理用ガスに関するものである。   The present invention relates to a carburizing method for a steel member and a carburizing gas used therefor.

鋼製部材の表面硬化方法の一つとして、ＲＸガス（浸炭処理用ガス）を用いた浸炭方法が知られている（例えば、特許文献１参照）。この浸炭方法におけるＲＸガス供給装置は、少量の酸素が含まれた窒素ガスを供給する窒素発生装置と、炭化水素ガスを供給する炭化水素供給装置と、所定の供給量に調整された窒素ガスと炭化水素ガスとが導入されて１次処理される低温反応槽と、１次処理ガスと所定の供給量に調整された炭化水素ガスとが導入されて混合される２次混合器とを有している。そして、その２次混合器でＲＸガスがつくられる。ここで、上記炭化水素供給装置としては、所定の容積を有する高圧容器に充填された液化高純度炭化水素を、気化して所望の供給圧に調整されて供給できる装置が用いられる。上記炭化水素の具体例としては、メタン，エタン，プロパン，ブタン等のパラフィン系の炭化水素があげられる。そして、ＲＸガスの原料には、上記のように、メタン（天然ガス）等が使用されることから、ＲＸガスの組成は、一酸化炭素ガス（ＣＯ）：２０〜２５モル％、水素ガス（Ｈ2 ）：３０〜４０モル％、残りが窒素ガス（Ｎ2 ）となっている。 As one surface hardening method for steel members, a carburizing method using RX gas (carburizing gas) is known (for example, see Patent Document 1). The RX gas supply device in this carburizing method includes a nitrogen generator for supplying nitrogen gas containing a small amount of oxygen, a hydrocarbon supply device for supplying hydrocarbon gas, and a nitrogen gas adjusted to a predetermined supply amount, A low-temperature reaction vessel in which hydrocarbon gas is introduced and subjected to primary treatment, and a secondary mixer in which the primary treatment gas and hydrocarbon gas adjusted to a predetermined supply amount are introduced and mixed ing. And RX gas is made with the secondary mixer. Here, as the hydrocarbon supply device, a device capable of vaporizing liquefied high-purity hydrocarbon filled in a high-pressure vessel having a predetermined volume and adjusting the supply pressure to a desired supply pressure is used. Specific examples of the hydrocarbon include paraffinic hydrocarbons such as methane, ethane, propane, and butane. As described above, methane (natural gas) or the like is used as the raw material for the RX gas. Therefore, the composition of the RX gas is carbon monoxide gas (CO): 20 to 25 mol%, hydrogen gas ( H 2): 30 to 40 mol%, which is balance and nitrogen gas (N 2).

ところで、上記ＲＸガスを用いた浸炭方法は、ガス浸炭法であり、真空浸炭法に比べ、浸炭速度が遅く、単位時間当たりの処理個数が少ない。   By the way, the carburizing method using the RX gas is a gas carburizing method, and has a lower carburizing speed and a smaller number of treatments per unit time than the vacuum carburizing method.

特開２０１２−３２１１３号公報JP 2012-32113 A

ガス浸炭法を用いた浸炭方法は、先に述べたように、浸炭速度が遅いことから、生産性向上のため、浸炭速度の向上が求められている。   Since the carburizing method using the gas carburizing method has a low carburizing rate as described above, an improvement in the carburizing rate is required to improve productivity.

本発明は、このような事情に鑑みなされたもので、浸炭速度を速めることができる浸炭方法およびそれに用いる浸炭処理用ガスの提供をその目的とする。   The present invention has been made in view of such circumstances, and an object thereof is to provide a carburizing method capable of increasing the carburizing speed and a carburizing gas used therefor.

上記の目的を達成するため、本発明は、少なくとも一酸化炭素ガスと水素ガスとを含む浸炭処理用ガスを用いる浸炭方法であって、その浸炭処理用ガスにおける一酸化炭素ガスの濃度を、３０〜６０モル％の範囲内に設定する浸炭方法を第１の要旨とする。   In order to achieve the above object, the present invention provides a carburizing method using a carburizing gas containing at least carbon monoxide gas and hydrogen gas, wherein the concentration of carbon monoxide gas in the carburizing gas is 30 The carburizing method set in the range of ˜60 mol% is the first gist.

また、本発明は、上記第１の要旨の浸炭方法に用いる浸炭処理用ガスであって、少なくとも一酸化炭素ガスと水素ガスとを含み、その一酸化炭素ガスの濃度が３０〜６０モル％の範囲内に設定されている浸炭処理用ガスを第２の要旨とする。   Further, the present invention is a carburizing gas used in the carburizing method according to the first aspect, which includes at least carbon monoxide gas and hydrogen gas, and the concentration of the carbon monoxide gas is 30 to 60 mol%. The carburizing gas set within the range is the second gist.

本発明者は、浸炭速度を速くすべく、浸炭処理用ガスの組成について、研究を重ねた。その過程で、一酸化炭素ガスの濃度が高くなるにつれて浸炭速度が速くなることを突き止めた。また、水素ガスの濃度が浸炭速度に影響を及ぼし、水素ガスの濃度をある程度まで高くすると浸炭速度が速くなるが、それよりも高くすると逆に浸炭速度が遅くなることも突き止めた。そして、さらに研究を重ねた結果、一酸化炭素ガスの濃度を、従来よりも高く３０〜６０モル％の範囲内に設定すると、それに伴い、水素ガスも適度（３５〜５５モル％）に存在するようになり、浸炭速度が向上することを見出し、本発明に到達した。   The present inventor conducted research on the composition of the carburizing gas in order to increase the carburizing rate. In the process, it was found that the carburization rate increased as the concentration of carbon monoxide gas increased. It was also found that the concentration of hydrogen gas has an effect on the carburization rate, and that the carburization rate increases when the hydrogen gas concentration is increased to some extent, but conversely the carburization rate decreases when the concentration is higher. As a result of further research, when the concentration of carbon monoxide gas is set to be in the range of 30 to 60 mol%, which is higher than before, hydrogen gas is also present moderately (35 to 55 mol%). As a result, it was found that the carburization rate was improved, and the present invention was reached.

本発明の浸炭方法は、浸炭処理用ガスにおける一酸化炭素ガスの濃度を、３０〜６０モル％の比較的高濃度の範囲内に設定するため、従来の浸炭方法よりも一酸化炭素ガスの濃度が高く、浸炭速度を速くすることができる。   In the carburizing method of the present invention, the concentration of carbon monoxide gas in the carburizing gas is set within a relatively high concentration range of 30 to 60 mol%, so that the concentration of carbon monoxide gas is higher than that of the conventional carburizing method. The carburization rate can be increased.

上記浸炭処理用ガスにおける一酸化炭素ガスと水素ガスとの濃度比を、１：１に設定する場合には、一酸化炭素ガスと水素ガスの濃度がより適正化され、浸炭速度をより速めることができる。   When the concentration ratio of carbon monoxide gas and hydrogen gas in the carburizing gas is set to 1: 1, the concentration of carbon monoxide gas and hydrogen gas is more optimized, and the carburization rate is increased. Can do.

なお、上記「１：１」は、ガスの濃度比であるため、正確な「１：１」だけではなく、±５％の誤差の範囲〔「（０．９５〜１．０５）：１」または「１：（０．９５〜１．０５）」〕も含む意味である。   Since “1: 1” is a gas concentration ratio, not only accurate “1: 1” but also an error range of ± 5% [“(0.95 to 1.05): 1” Or “1: (0.95 to 1.05)”].

また、本発明の浸炭処理用ガスは、少なくとも一酸化炭素ガスと水素ガスとを含み、その一酸化炭素ガスの濃度が３０〜６０モル％の範囲内に設定されているため、従来の浸炭処理用ガスよりも一酸化炭素ガスの濃度が高く、浸炭速度を速くすることができる。   Further, the carburizing gas of the present invention includes at least carbon monoxide gas and hydrogen gas, and the concentration of the carbon monoxide gas is set within a range of 30 to 60 mol%, so that the conventional carburizing treatment is performed. The concentration of carbon monoxide gas is higher than that of the working gas, and the carburization rate can be increased.

本発明の浸炭方法に用いる浸炭処理用ガスの製造設備の第１の実施の形態を模式的に示す構成図である。It is a block diagram which shows typically 1st Embodiment of the manufacturing equipment of the carburizing process gas used for the carburizing method of this invention. 浸炭処理用ガス製造設備の第２の実施の形態を模式的に示す構成図である。It is a block diagram which shows typically 2nd Embodiment of the gas manufacturing equipment for carburizing treatment. 浸炭処理用ガス製造設備の第３の実施の形態を模式的に示す構成図である。It is a block diagram which shows typically 3rd Embodiment of the gas manufacturing equipment for carburizing treatment. 浸炭処理用ガス製造設備の第４の実施の形態を模式的に示す構成図である。It is a block diagram which shows typically 4th Embodiment of the gas manufacturing equipment for carburizing treatment.

つぎに、本発明の実施の形態を図面にもとづいて詳しく説明する。   Next, embodiments of the present invention will be described in detail with reference to the drawings.

図１は、本発明の浸炭方法に用いる浸炭処理用ガスの製造設備の第１の実施の形態を示す構成図である。この実施の形態では、その浸炭処理用ガス製造設備は、得られる浸炭処理用ガスが、一酸化炭素ガスの濃度も水素ガスの濃度も略５０モル％となるようにするものである。   FIG. 1 is a configuration diagram showing a first embodiment of a carburizing gas production facility used in the carburizing method of the present invention. In this embodiment, the carburizing gas production facility is such that the obtained carburizing gas has a carbon monoxide gas concentration and a hydrogen gas concentration of approximately 50 mol%.

すなわち、上記浸炭処理用ガス製造設備は、天然ガス（多量のメタンガスと少量のエタンガス，プロパンガス，硫黄等からなる）を第１ヒータ１で加熱してから、脱硫器２に通し、管路Ａに送るようになっている。そして、酸素ガスを第２ヒータ３で加熱し管路Ｂに送るようになっている。この管路Ｂは、管路Ａと連結され、上記天然ガスと上記酸素ガスとが混合した状態になる。ついで、その混合ガスを改質器４に通し、高濃度の一酸化炭素ガスと水素ガスとを生成させ、管路Ｃに通すようになっている。このとき、同時に、二酸化炭素ガスおよび水蒸気も生成される。つづいて、それらを冷却器５に通した後、気液分離器６で気液分離し、気液分離された後の液体を排水管路から外部に排水し、気体を圧縮機吸込ホルダ７に通してから圧縮機８で圧縮し、管路Ｄに通すようになっている。その後、その圧縮機８で圧縮された気体を、圧力スイング吸着装置９に通し、上記一酸化炭素ガスと水素ガスの濃度を、いずれも略５０モル％に高め、管路Ｅを経由し、ＲＸガスとして、図示していない従来公知の浸炭炉に供給するようになっている。そして、圧力スイング吸着装置９に吸着させた二酸化炭素ガスを、真空ポンプ１０を利用して脱着させ、フレアスタック１３で焼却するようになっている。なお、図において、符号Ｖは弁を示す。   That is, the carburizing treatment gas production facility uses natural gas (consisting of a large amount of methane gas and a small amount of ethane gas, propane gas, sulfur, etc.) heated by the first heater 1 and then passed through the desulfurizer 2 to the pipe A To send to. The oxygen gas is heated by the second heater 3 and sent to the pipe B. The pipe B is connected to the pipe A, and the natural gas and the oxygen gas are mixed. Next, the mixed gas is passed through the reformer 4 to generate high-concentration carbon monoxide gas and hydrogen gas, which are then passed through the pipe C. At the same time, carbon dioxide gas and water vapor are also generated. Subsequently, after passing them through the cooler 5, gas-liquid separation is performed by the gas-liquid separator 6, the liquid after the gas-liquid separation is drained to the outside from the drain pipe, and the gas is supplied to the compressor suction holder 7. After being passed, it is compressed by the compressor 8 and passed through the pipe D. Thereafter, the gas compressed by the compressor 8 is passed through the pressure swing adsorption device 9, and the concentrations of the carbon monoxide gas and the hydrogen gas are both increased to about 50 mol%. As gas, it supplies to the conventionally well-known carburizing furnace which is not illustrated. The carbon dioxide gas adsorbed by the pressure swing adsorption device 9 is desorbed by using the vacuum pump 10 and incinerated by the flare stack 13. In the figure, the symbol V indicates a valve.

ここで、上記圧力スイング吸着装置９で得られた略５０モル％の一酸化炭素ガスと水素ガスとが、先に述べたように、浸炭処理用ガスとして浸炭炉で用いられる。このような浸炭処理用ガスを用いることにより、浸炭速度を速めることができる。   Here, approximately 50 mol% of carbon monoxide gas and hydrogen gas obtained by the pressure swing adsorption device 9 are used in the carburizing furnace as the carburizing gas as described above. By using such a carburizing gas, the carburizing speed can be increased.

図２は、上記浸炭処理用ガス製造設備の第２の実施の形態を示す構成図である。この実施の形態の浸炭処理用ガス製造設備は、上記第１の実施の形態（図１参照）において、水素ガスの管路と二酸化炭素ガスの管路を追加している。すなわち、天然ガスの管路に水素ガスの管路を連結し、天然ガスと水素ガスとを混合した後、第１ヒータ１で加熱してから、脱硫器２に通し、管路Ａに送るようになっている。そして、酸素ガスの管路に二酸化炭素ガスの管路を連結し、酸素ガスと二酸化炭素ガスとを混合してから第２ヒータ３で加熱し管路Ｂに送るようになっている。この管路Ｂでは、上記天然ガスを含む混合ガスと、上記酸素ガスを含む混合ガスとが混合した状態になる。また、この実施の形態の浸炭処理用ガス製造設備は、上記第１の実施の形態（図１参照）において、真空ポンプ１０とフレアスタック１３との間に分岐する管路Ｆを追加している。すなわち、圧力スイング吸着装置９に吸着させた二酸化炭素ガスを、真空ポンプ１０を利用して脱着させ、その大部分を管路Ｆに送り、圧縮機吸込ホルダ１１に通してから圧縮機１２で圧縮し、原料の一部として再利用し、残部をフレアスタック１３で焼却するようになっている。   FIG. 2 is a configuration diagram showing a second embodiment of the carburizing gas production facility. The carburizing gas production facility of this embodiment is additionally provided with a hydrogen gas conduit and a carbon dioxide gas conduit in the first embodiment (see FIG. 1). That is, a hydrogen gas line is connected to a natural gas line, and after mixing natural gas and hydrogen gas, the gas is heated by the first heater 1 and then passed through the desulfurizer 2 and sent to the line A. It has become. A carbon dioxide gas pipe is connected to the oxygen gas pipe, and the oxygen gas and the carbon dioxide gas are mixed and then heated by the second heater 3 and sent to the pipe B. In this pipeline B, the mixed gas containing the natural gas and the mixed gas containing the oxygen gas are mixed. In addition, the carburizing gas production facility of this embodiment is additionally provided with a pipe F that branches between the vacuum pump 10 and the flare stack 13 in the first embodiment (see FIG. 1). . That is, carbon dioxide gas adsorbed by the pressure swing adsorption device 9 is desorbed by using the vacuum pump 10, most of the carbon dioxide gas is sent to the pipe F, passed through the compressor suction holder 11, and then compressed by the compressor 12. However, it is reused as a part of the raw material, and the remainder is incinerated by the flare stack 13.

図３は、上記浸炭処理用ガス製造設備の第３の実施の形態を示す構成図である。この実施の形態の浸炭処理用ガス製造設備は、上記第２の実施の形態（図２参照）において、液体窒素タンク２０を追加し、その液体窒素を気化させた窒素ガスを、上記圧力スイング吸着装置９で得られた略５０モル％の一酸化炭素ガスと水素ガスとの混合ガスに混合するようにしたものである。それ以外の部分は、上記第２の実施の形態と同様であり、同様の部分には同じ符号を付している。   FIG. 3 is a configuration diagram showing a third embodiment of the carburizing gas production facility. The carburizing gas production facility of this embodiment is the same as that of the second embodiment (see FIG. 2), except that a liquid nitrogen tank 20 is added and the nitrogen gas obtained by vaporizing the liquid nitrogen is absorbed by the pressure swing adsorption. The mixed gas of about 50 mol% carbon monoxide gas and hydrogen gas obtained by the apparatus 9 is mixed. Other parts are the same as those in the second embodiment, and the same reference numerals are given to the same parts.

この実施の形態では、上記液体窒素タンク２０からの窒素ガスを混合することにより、浸炭処理用ガスの一酸化炭素ガスの濃度を、処理対象物に応じて、上記略５０モル％から薄めるように調整することができる。なお、一酸化炭素ガスの濃度の下限値は３０モル％である。このような浸炭処理用ガスを用いることにより、浸炭対象品の材質や厚み等に応じて一酸化炭素ガスの濃度を調節し、最適な浸炭を行うことができる。   In this embodiment, by mixing the nitrogen gas from the liquid nitrogen tank 20, the concentration of the carbon monoxide gas for carburizing treatment gas is reduced from about 50 mol% according to the object to be treated. Can be adjusted. The lower limit of the concentration of carbon monoxide gas is 30 mol%. By using such a carburizing gas, the concentration of carbon monoxide gas can be adjusted according to the material, thickness, etc. of the carburized object, and optimum carburizing can be performed.

図４は、上記浸炭処理用ガス製造設備の第４の実施の形態を示す構成図である。この実施の形態の浸炭処理用ガス製造設備は、従来のＲＸガス製造設備３０または図２に示す浸炭処理用ガス製造設備に、一酸化炭素ガス容器３１を追加し、その一酸化炭素ガスを、従来のＲＸガス（一酸化炭素ガス：２０〜２５モル％）または図２に示す浸炭処理用ガス製造設備で得られたＲＸガスに混合し、一酸化炭素ガスの高濃度化を可能にしたものである。   FIG. 4 is a configuration diagram showing a fourth embodiment of the carburizing gas production facility. The carburizing gas production facility of this embodiment includes a carbon monoxide gas container 31 added to the conventional RX gas production facility 30 or the carburizing gas production facility shown in FIG. Mixing with conventional RX gas (carbon monoxide gas: 20 to 25 mol%) or RX gas obtained at the carburizing gas production facility shown in FIG. 2, enabling high concentration of carbon monoxide gas It is.

この実施の形態では、上記一酸化炭素ガスを混合することにより、先に述べたように、ＲＸガスにおける一酸化炭素ガスの濃度を高めて改質ＲＸガスとし、浸炭対象品の材質や厚み等に応じて、３０〜６０モル％の範囲内で調整することができる。このような浸炭処理用ガスを用いることにより、浸炭速度を速めることができる。また、図２に示す浸炭処理用ガス製造設備で得られたＲＸガスが濃度不足だったり、浸炭対象品が変わってより高濃度のものが求められる場合等に、迅速に対応することができるようになる。   In this embodiment, by mixing the carbon monoxide gas, as described above, the concentration of the carbon monoxide gas in the RX gas is increased to obtain a modified RX gas, and the material, thickness, etc. of the carburized object Depending on, it can be adjusted within the range of 30 to 60 mol%. By using such a carburizing gas, the carburizing speed can be increased. In addition, when the RX gas obtained at the carburizing gas production facility shown in FIG. 2 is insufficient in concentration, or when a carburized product is changed and a higher concentration is required, it can be quickly handled. become.

つぎに、実施例について比較例と併せて説明する。但し、本発明は、実施例に限定されるわけではない。   Next, examples will be described together with comparative examples. However, the present invention is not limited to the examples.

〔実施例１〜３および比較例１，２〕
日本工業規格（ＪＩＳ）で規定されるＳＵＳ３１６（Ｃｒ含有１８重量％，Ｎｉ含有１２重量％，Ｍｏ含有２．５重量％，残部Ｆｅ）の２．５ｍｍ厚板片を準備し、それを浸炭炉に入れ、４５０℃まで加熱し、下記の表１に示す組成のＲＸガスを用いて浸炭処理した。その浸炭処理は、表面硬度が８７０〜８９０Ｈｖ、浸炭層の深さが２０μｍになるように行った。そして、その浸炭処理に要した時間を測定した。その結果を下記の表１に示した。 [Examples 1 to 3 and Comparative Examples 1 and 2]
A 2.5 mm thick plate of SUS316 (18% by weight of Cr, 12% by weight of Ni, 2.5% by weight of Mo, and the remainder of Fe) stipulated by Japanese Industrial Standards (JIS) is prepared and the carburizing furnace And heated to 450 ° C. and carburized using RX gas having the composition shown in Table 1 below. The carburizing treatment was performed so that the surface hardness was 870 to 890 Hv and the depth of the carburized layer was 20 μm. And the time required for the carburizing process was measured. The results are shown in Table 1 below.

Figure 2014237868
Figure 2014237868

上記の結果から、ＲＸガスの一酸化炭素ガスの濃度が３０〜６０モル％である実施例１〜３は、一酸化炭素ガスの濃度が２５モル％と低い比較例１と比較して、浸炭速度が速いことがわかる。なかでも、一酸化炭素ガスの濃度も水素ガスの濃度も５０モル％である実施例２が最も速いことがわかる。また、比較例２のように、一酸化炭素ガスの濃度を６５モル％と高くし過ぎても、水素ガスの濃度が３５モル％と低くなるため、浸炭速度が遅くなることがわかる。   From the above results, Examples 1 to 3 in which the concentration of carbon monoxide gas in RX gas is 30 to 60 mol% are carburized compared to Comparative Example 1 in which the concentration of carbon monoxide gas is as low as 25 mol%. You can see that the speed is fast. In particular, Example 2 in which the concentration of carbon monoxide gas and the concentration of hydrogen gas are 50 mol% is the fastest. In addition, as in Comparative Example 2, it can be seen that even if the concentration of the carbon monoxide gas is made too high, such as 65 mol%, the concentration of hydrogen gas becomes as low as 35 mol%, so that the carburization rate becomes slow.

本発明は、浸炭速度を速めることに利用することができる。   The present invention can be used to increase the carburization rate.

１ 第１ヒータ
３ 第２ヒータ
４ 改質器
９ 圧力スイング吸着装置 DESCRIPTION OF SYMBOLS 1 1st heater 3 2nd heater 4 Reformer 9 Pressure swing adsorption device

Claims (3)

少なくとも一酸化炭素ガスと水素ガスとを含む浸炭処理用ガスを用いる浸炭方法であって、その浸炭処理用ガスにおける一酸化炭素ガスの濃度を、３０〜６０モル％の範囲内に設定することを特徴とする浸炭方法。   A carburizing method using a carburizing gas containing at least carbon monoxide gas and hydrogen gas, wherein the concentration of the carbon monoxide gas in the carburizing gas is set within a range of 30 to 60 mol%. Characterized carburizing method. 上記浸炭処理用ガスにおける一酸化炭素ガスと水素ガスとの濃度比を、１：１に設定する請求項１記載の浸炭方法。   The carburizing method according to claim 1, wherein a concentration ratio of carbon monoxide gas to hydrogen gas in the carburizing gas is set to 1: 1. 上記請求項１または２記載の浸炭方法に用いる浸炭処理用ガスであって、少なくとも一酸化炭素ガスと水素ガスとを含み、その一酸化炭素ガスの濃度が３０〜６０モル％の範囲内に設定されていることを特徴とする浸炭処理用ガス。   A carburizing gas used in the carburizing method according to claim 1 or 2, comprising at least carbon monoxide gas and hydrogen gas, and the concentration of the carbon monoxide gas is set within a range of 30 to 60 mol%. A carburizing gas characterized by
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JP2004332080A (en) * 2003-05-12 2004-11-25 Koyo Thermo System Kk Method and device for generating atmospheric gas for carburizing
JP2005200695A (en) * 2004-01-14 2005-07-28 Onex Corp Gas carburizing method
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