JP2008189988A - Surface-coated member, and method for producing the same - Google Patents
Surface-coated member, and method for producing the same Download PDFInfo
- Publication number
- JP2008189988A JP2008189988A JP2007025048A JP2007025048A JP2008189988A JP 2008189988 A JP2008189988 A JP 2008189988A JP 2007025048 A JP2007025048 A JP 2007025048A JP 2007025048 A JP2007025048 A JP 2007025048A JP 2008189988 A JP2008189988 A JP 2008189988A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- alloy
- bath
- mass
- carbide layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
Description
本発明は、鋼または合金鋼からなる部材の表面にCrを含有する複合炭化物層を形成した表面被覆部材およびその製造方法に関するものである。 The present invention relates to a surface-coated member in which a composite carbide layer containing Cr is formed on the surface of a member made of steel or alloy steel, and a method for manufacturing the same.
鋼や合金鋼からなる各種部材の表面に、単層の炭化物を形成することによって、部材の耐摩耗性，耐溶融アルミ性が著しく向上することは従来から広く知られており、工業的に様々な分野で使用されている。
部材の表面に単層の炭化物を形成する技術としては、炭化物を形成する元素を含む金属粉末と硼砂とからなる溶融浴に部材を浸漬する技術が一般的である。あるいは、炭化物を形成する元素を含む酸化物と硼砂に加えて、Al，Ca，Si等の還元剤を添加した溶融浴に部材を浸漬することによって、表面に単層の炭化物を形成する技術が検討されている（特許文献１参照）。
It has been widely known that, by forming a single layer of carbide on the surface of various members made of steel or alloy steel, the wear resistance and molten aluminum resistance of the member are remarkably improved. Used in various fields.
As a technique for forming a single layer of carbide on the surface of the member, a technique in which the member is immersed in a molten bath made of metal powder containing an element that forms carbide and borax is common. Alternatively, there is a technique for forming a single layer of carbide on the surface by immersing the member in a molten bath containing a reducing agent such as Al, Ca, Si in addition to oxide and borax containing elements that form carbide. It has been studied (see Patent Document 1).
また、２種以上の炭化物形成元素を含む金属粉末と硼砂とからなる溶融浴に部材を浸漬することによって、表面に複合炭化物層を形成する技術が検討されている（非特許文献１参照）。
これらの技術は、いずれも
(A)部材に残留した溶融浴液の洗浄が困難である、
(B)溶融浴から取り出した部材を冷却する過程で、部材が容易に酸化される
等の問題があった。
All of these technologies
(A) It is difficult to wash the molten bath liquid remaining on the member.
(B) In the process of cooling the member taken out from the molten bath, there was a problem that the member was easily oxidized.
本発明は、鉄または鉄合金からなる部材の表面にCrを含有する複合炭化物層を形成した表面被覆部材、およびその製造方法を提供することを目的とする。特に本発明の製造方法を適用すれば、表面被覆部材の製造過程で、上記の(A)の問題点を解消して洗浄時間を短縮することによる生産効率の向上，および(B)の問題点を解消して表面被覆部材の表面性状を改善することによる歩留りの向上を達成できる。 An object of the present invention is to provide a surface-coated member in which a composite carbide layer containing Cr is formed on the surface of a member made of iron or an iron alloy, and a method for manufacturing the same. In particular, if the production method of the present invention is applied, in the production process of the surface covering member, the problem of the above (A) is solved and the production time is improved by reducing the cleaning time, and the problem of (B) The yield can be improved by eliminating the above and improving the surface properties of the surface covering member.
本発明は、下記の(a)群，(b)群および(c)群の粉体からなる溶融塩浴中に、所定の形状を有する部材を浸漬して、部材の表面にクロムを含有する複合炭化物層を形成する表面被覆部材の製造方法である。
(a)Ti，Ｖ，NbおよびTaの中から選ばれる２種以上の金属元素を含む金属粉末
(b)Crを含むクロム粉末
(c)硼砂
本発明の表面被覆部材の製造方法においては、金属粉末がTi粉末，スポンジチタン粉末，Fe−Ti合金粉末，Fe−Nb合金粉末，Fe−Ｖ合金粉末およびFe−Ta合金粉末の中から選ばれる２種以上であり、クロム粉末がCr粉末およびFe−Cr合金粉末の中から選ばれる１種であることが好ましい。また、溶融塩浴に金属元素の塩化物粉末および／または酸化物粉末を添加することが好ましい。
In the present invention, a member having a predetermined shape is immersed in a molten salt bath composed of powders of the following groups (a), (b) and (c), and chromium is contained on the surface of the member. It is a manufacturing method of the surface covering member which forms a composite carbide layer.
(a) Metal powder containing two or more metal elements selected from Ti, V, Nb and Ta
(b) Cr powder containing Cr
(c) Borax In the method for producing a surface-coated member of the present invention, the metal powder is Ti powder, sponge titanium powder, Fe-Ti alloy powder, Fe-Nb alloy powder, Fe-V alloy powder and Fe-Ta alloy powder. It is preferable that the chromium powder is one or more selected from among Cr powder and Fe—Cr alloy powder. Further, it is preferable to add metal element chloride powder and / or oxide powder to the molten salt bath.
なお、酸化物粉末を添加する場合は、溶融塩浴にAl，Si，Ｂ4Ｃ，Ca−Si合金，Fe−Si合金およびFe−Ｂ合金の中から選ばれる１種または２種以上を含む粉末を還元剤として添加することが好ましい。さらに塩化物粉末がＶCl3，TaCl5，NbCl5およびCrCl3の中から選ばれる１種または２種以上の粉末であり、酸化物粉末がＶ2Ｏ5，Nb2Ｏ5，Ta2Ｏ5およびTiＯ2の中から選ばれる１種または２種以上の粉末であることが好ましい。 When the oxide powder is added, the molten salt bath contains one or more selected from Al, Si, B 4 C, Ca—Si alloy, Fe—Si alloy and Fe—B alloy. It is preferable to add powder as a reducing agent. Furthermore, the chloride powder is one or more powders selected from VCl 3 , TaCl 5 , NbCl 5 and CrCl 3 , and the oxide powder is V 2 O 5 , Nb 2 O 5 , Ta 2 O 5. And one or more powders selected from TiO 2 are preferred.
本発明の表面被覆部材の製造方法は、鋼または合金鋼を所定の形状に加工した部材に適用することが好ましい。
また本発明は、所定の形状を有する部材の表面に、Ti，Ｖ，NbおよびTaの中から選ばれる１種または２種以上の金属元素とCrからなる複合炭化物層を有する表面被覆部材である。
The method for producing a surface-coated member of the present invention is preferably applied to a member obtained by processing steel or alloy steel into a predetermined shape.
Moreover, this invention is a surface covering member which has the composite carbide layer which consists of 1 type, or 2 or more types of metal elements chosen from Ti, V, Nb, and Ta, and Cr on the surface of the member which has a defined shape. .
本発明の表面被覆部材の材料となる部材は、鋼または合金鋼を所定の形状に加工したものであることが好ましい。 It is preferable that the member used as the material of the surface covering member of the present invention is obtained by processing steel or alloy steel into a predetermined shape.
本発明によれば、所定の形状を有する部材の表面にCrを含有する複合炭化物層を形成した表面被覆部材を得ることができる。
その表面被覆部材は、様々な工業分野で使用できる。たとえば、
(1)プレス加工：曲げ加工パンチとダイ，打ち抜きパンチとダイ，絞り加工ダイ，剪断パンチ
(2)線材：ガイドロール，引抜きダイス
(3)鋼管：マンドレルミルロール，スクイズロール，引き抜きダイス
(4)冷間鍛造：据え込みパンチとダイ，後方押し出しパンチ
(5)熱間鍛造：密閉鍛造ダイ，アップセッターダイ
(6)鋳造：ダイカストピン，鋳型，入れ子型
(7)ゴム，ブラスチック，ガラス：成形ダイ
(8)その他：カム，軸受け，ピン
などに好適である。
According to the present invention, a surface-coated member in which a composite carbide layer containing Cr is formed on the surface of a member having a predetermined shape can be obtained.
The surface covering member can be used in various industrial fields. For example,
(1) Pressing: bending punch and die, punch and die, drawing die, shear punch
(2) Wire: Guide roll, drawing die
(3) Steel pipe: Mandrel mill roll, squeeze roll, drawing die
(4) Cold forging: Upset punch and die, rear extrusion punch
(5) Hot forging: closed forging die, upsetter die
(6) Casting: Die-cast pins, molds, nested molds
(7) Rubber, plastic, glass: molding die
(8) Others: Suitable for cams, bearings, pins, etc.
本発明では、表面被覆部材を製造するにあたって溶融塩浴に、所定の形状を有する鋼または合金鋼からなる部材を浸漬する。溶融塩浴にはTi，Ｖ，NbおよびTaの中から選ばれる２種以上の金属元素を含む金属粉末を添加する。Ti，Ｖ，Nb，Taを添加するために使用する金属粉末は、Ti粉末，スポンジチタン粉末，Fe−Ti合金粉末，Fe−Nb合金粉末，Fe−Ｖ合金粉末，Fe−Ta合金粉末の中から適宜選択するのが好ましい。さらにCrを含む粉末（以下、クロム粉末という）を溶融塩浴に添加する。ただし、クロム粉末を添加しなくても良い場合もある。 In the present invention, in manufacturing the surface covering member, a member made of steel or alloy steel having a predetermined shape is immersed in a molten salt bath. A metal powder containing two or more metal elements selected from Ti, V, Nb and Ta is added to the molten salt bath. The metal powder used for adding Ti, V, Nb, Ta is Ti powder, sponge titanium powder, Fe-Ti alloy powder, Fe-Nb alloy powder, Fe-V alloy powder, Fe-Ta alloy powder. It is preferable to select appropriately. Further, a powder containing Cr (hereinafter referred to as chromium powder) is added to the molten salt bath. However, it may not be necessary to add chromium powder.
これらの金属元素を含む粉末は、塩化物粉末や酸化物粉末として添加することが好ましい。その場合、塩化物粉末と酸化物粉末のうちのいずれか片方のみを使用しても良いし、あるいは両方を併用しても良い。塩化物粉末は、ＶCl3，TaCl5，NbCl5およびCrCl3の中から選ばれる２種以上の粉末を使用することが好ましい。酸化物粉末は、Ｖ2Ｏ5，Nb2Ｏ5，Ta2Ｏ5およびTiＯ2の中から選ばれる２種以上の粉末を使用することが好ましい。 The powder containing these metal elements is preferably added as a chloride powder or an oxide powder. In that case, only one of the chloride powder and the oxide powder may be used, or both may be used in combination. As the chloride powder, it is preferable to use two or more kinds of powders selected from VCl 3 , TaCl 5 , NbCl 5 and CrCl 3 . As the oxide powder, it is preferable to use two or more kinds of powders selected from V 2 O 5 , Nb 2 O 5 , Ta 2 O 5 and TiO 2 .
また、酸化物粉末を溶融塩浴に添加する場合は、還元剤を併用することが好ましい。還元剤は、Al，Si，Ｂ4 Ｃ，Ca−Si合金，Fe−Si合金およびFe−Ｂ合金の中から選ばれる粉末を使用することが好ましい。一方、Mg，Zr，Caは、溶融塩浴の粘性が著しく高くなり、浸漬して複合炭化物層を形成した表面被覆部材の洗浄に長時間を要するので、実用上は好ましくない。 Moreover, when adding oxide powder to a molten salt bath, it is preferable to use a reducing agent together. Reducing agent, Al, Si, B 4 C , Ca-Si alloy, it is preferable to use a powder selected from the group consisting of Fe-Si alloys and Fe-B alloy. On the other hand, Mg, Zr, and Ca are not practically preferable because the viscosity of the molten salt bath is remarkably high, and it takes a long time to clean the surface covering member that has been immersed to form the composite carbide layer.
ただし、Mg，Zr，Caを使用する場合は、ハロゲン化物（たとえばNaCl，ＫCl，NaＦ等），酸化物（たとえばＰ2Ｏ5等），水酸化物（たとえばNaＯＨ，ＫＯＨ等），硫酸塩，炭酸塩を添加して融点を下げることによって、溶融塩浴の粘性を低下させることは可能である。しかし、これらの物質は腐食性を有するので、大量に添加することは好ましくない。
溶融塩浴に添加する金属粉末，クロム粉末，それらの塩化物粉末および酸化物粉末と還元剤の粒子の形状は特に限定しないが、粉末状，球状あるいは薄片状のものを使用することが好ましい。溶融塩浴では、これらの粒子の他に、硼砂（Na2Ｂ4Ｏ5）を使用する。硼砂は、通常、粉末である。
However, when using Mg, Zr, Ca, halide (for example, NaCl, KCl, NaF, etc.), oxide (for example, P 2 O 5 etc.), hydroxide (for example, NaOH, KOH, etc.), sulfate, It is possible to reduce the viscosity of the molten salt bath by adding carbonate to lower the melting point. However, since these substances are corrosive, it is not preferable to add them in large quantities.
There are no particular limitations on the shape of the metal powder, chromium powder, chloride powder, oxide powder and reducing agent particles added to the molten salt bath, but it is preferable to use powder, spherical or flakes. In addition to these particles, borax (Na 2 B 4 O 5 ) is used in the molten salt bath. Borax is usually a powder.
溶融塩浴の温度が低すぎると、複合炭化物層を形成に長時間を要する。一方、高すぎると、浴容器の耐久性が低下する。したがって、溶融塩浴の温度は700〜1250℃の範囲内が好ましい。より好ましくは、850〜1100℃である。
以上のような溶融塩浴に、所定の形状を有する部材を浸漬ことによって、表面にTi，Ｖ，NbおよびTaの中から選ばれる２種以上の金属元素とCrからなる複合炭化物層を有する表面被覆部材を得ることができる。
If the temperature of the molten salt bath is too low, it takes a long time to form the composite carbide layer. On the other hand, when too high, durability of a bath container will fall. Therefore, the temperature of the molten salt bath is preferably in the range of 700 to 1250 ° C. More preferably, it is 850-1100 degreeC.
Surface having a composite carbide layer composed of two or more metal elements selected from Ti, V, Nb and Ta and Cr by immersing a member having a predetermined shape in the molten salt bath as described above A covering member can be obtained.
表面被覆部材の材料となる部材は、鉄合金，超硬合金，ニッケル合金，コバルト合金，サーメット，炭素材，鋼，合金鋼等の様々な素材からなるものを使用できる。ただし、上記の(a)〜(h)の用途に使用されるパンチ，ダイ，ロール等の部材としては、鋼や合金鋼からなるものが多量に使用されている。したがって表面被覆部材の材料となる部材は、鋼や合金鋼を所定の形状に加工したものであることが好ましい。 The member used as the material of the surface covering member can be made of various materials such as iron alloy, cemented carbide, nickel alloy, cobalt alloy, cermet, carbon material, steel, and alloy steel. However, as members such as punches, dies, and rolls used for the above-mentioned applications (a) to (h), a large amount of steel or alloy steel is used. Therefore, it is preferable that the member used as the material of the surface covering member is obtained by processing steel or alloy steel into a predetermined shape.
＜実施例１＞
鋼製の容器に無水硼砂を入れ、容器ごと電気炉で加熱して硼砂を溶融させ、950℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を、浴全体の質量（硼砂と酸化物粉末と還元剤とクロム粉末の合計）に対して８質量％添加し、さらにNb2Ｏ5粉末を浴全体の質量に対して７質量％，還元剤としてＢ4Ｃ粉末を浴全体の質量に対して５質量％を添加した後、クロム粉末を浴全体の質量に対して３質量％を添加して溶融塩浴を準備した。
<Example 1>
Anhydrous borax was placed in a steel container and the entire container was heated in an electric furnace to melt the borax, and a bath at 950 ° C. was prepared. In this bath, 8% by mass of flaky V 2 O 5 powder is added to the total mass of the bath (total of borax, oxide powder, reducing agent and chromium powder), and Nb 2 O 5 powder is further added to the bath. 7% by mass with respect to the total mass, 5% by mass of B 4 C powder as a reducing agent with respect to the total mass of the bath, and then 3% by mass of chromium powder with respect to the total mass of the bath A molten salt bath was prepared.
この溶融塩浴中に、直径10mmの丸棒試験片（JIS-SKD11）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例１とする。
この発明例１の丸棒試験片を切断して、その断面を光学顕微鏡で観察した。その結果、丸棒試験片の表面に厚さ７μｍの複合炭化物層が形成されていることが確かめられた。
次に、その断面を走査型電子顕微鏡（いわゆるＳＥＭ）で観察した。その例を図１に示す。図１に示すように、複合炭化物層の３ケ所（すなわち表層部，中央部，深奥部）で成分を分析したところ、Ｖが63質量％，Nbが18質量％，Crが７質量％含有されており、残部はＣであった。
A 10 mm diameter round bar specimen (JIS-SKD11) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and washed with warm water. This is referred to as Invention Example 1.
The round bar test piece of Invention Example 1 was cut and the cross section was observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 7 μm was formed on the surface of the round bar test piece.
Next, the cross section was observed with a scanning electron microscope (so-called SEM). An example is shown in FIG. As shown in FIG. 1, when the components were analyzed at three locations of the composite carbide layer (that is, the surface layer portion, the central portion, and the deep portion), V was 63 mass%, Nb was 18 mass%, and Cr was 7 mass%. The balance was C.
さらに、複合炭化物層の表面にてＸ線回折を行なった。得られた回折線は、ＶＣの回折線と良く一致していた。
以上の結果から、CrとNbを含有するＶＣからなる複合炭化物層が形成されたと考えられる。
＜実施例２＞
実施例１と同様にして硼砂を溶融させ、1000℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を、浴全体の質量（硼砂と酸化物粉末と還元剤とクロム粉末の合計）に対して９質量％添加し、さらにNb2Ｏ5粉末を浴全体の質量に対して６質量％，還元剤として粒状のAl末を浴全体の質量に対して５質量％を添加した後、クロム粉末を浴全体の質量に対して５質量％を添加して溶融塩浴を準備した。
Further, X-ray diffraction was performed on the surface of the composite carbide layer. The obtained diffraction lines were in good agreement with the VC diffraction lines.
From the above results, it is considered that a composite carbide layer made of VC containing Cr and Nb was formed.
<Example 2>
Borax was melted in the same manner as in Example 1 to prepare a 1000 ° C. bath. In this bath, flaky V 2 O 5 powder was added in an amount of 9% by mass with respect to the total mass of the bath (total of borax, oxide powder, reducing agent and chromium powder), and Nb 2 O 5 powder was further added to the bath. After adding 6% by mass to the total mass and 5% by mass of granular Al powder as a reducing agent based on the total mass of the bath, add 5% by mass of chromium powder to the total mass of the bath. A molten salt bath was prepared.
この溶融塩浴中に、直径10mmの丸棒試験片（JIS-SKD11）を４時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例２とする。
この発明例２の丸棒試験片を切断して、その断面を光学顕微鏡で観察した。その結果、丸棒試験片の表面に厚さ８μｍの複合炭化物層が形成されていることが確かめられた。
次に、その断面をＸ線マイクロアナライザー（いわゆるＥＰＭＡ）で分析した。その線分析の例を図２に示す。図２に示すように、複合炭化物層にはＶが60質量％，Nbが16質量％，Crが５質量％含有されており、残部はＣであった。
A 10 mm diameter round bar specimen (JIS-SKD11) was immersed in this molten salt bath for 4 hours, taken out, air-cooled, and washed with warm water. This is referred to as Invention Example 2.
The round bar test piece of Invention Example 2 was cut and the cross section was observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 8 μm was formed on the surface of the round bar test piece.
Next, the cross section was analyzed with an X-ray microanalyzer (so-called EPMA). An example of the line analysis is shown in FIG. As shown in FIG. 2, the composite carbide layer contained 60 mass% V, 16 mass% Nb, 5 mass% Cr, and the balance was C.
さらに、複合炭化物層の表面にてＸ線回折を行なった。得られた回折線は、ＶＣの回折線と良く一致していた。
以上の結果から、CrとNbを含有するＶＣからなる複合炭化物層が形成されたと考えられる。
＜実施例３＞
実施例１と同様にして硼砂を溶融させ、1000℃の浴を作成した。この浴中にFe−Ｖ（JIS-１号フェロバナジウム）粉末を、浴全体の質量（硼砂と金属粉末と還元剤とクロム粉末の合計）に対して10質量％添加し、さらにTi粉末を浴全体の質量に対して８質量％，クロム粉末を浴全体の質量に対して５質量％を添加して溶融塩浴を準備した。
Further, X-ray diffraction was performed on the surface of the composite carbide layer. The obtained diffraction lines were in good agreement with the VC diffraction lines.
From the above results, it is considered that a composite carbide layer made of VC containing Cr and Nb was formed.
<Example 3>
Borax was melted in the same manner as in Example 1 to prepare a 1000 ° C. bath. 10% by mass of Fe-V (JIS-1 ferrovanadium) powder is added to the total mass of the bath (total of borax, metal powder, reducing agent and chromium powder), and Ti powder is added to the bath. A molten salt bath was prepared by adding 8% by mass with respect to the total mass and 5% by mass of chromium powder with respect to the total mass of the bath.
この溶融塩浴中に、50×50×10mmの板状試験片（JIS-SKD61）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例３とする。
この発明例３の板状試験片を切断して、その断面を光学顕微鏡で観察した。その結果、板状試験片の表面に厚さ６μｍの複合炭化物層が形成されていることが確かめられた。
次に、複合炭化物層の成分を分析したところ、Ｖが62質量％，Tiが12質量％，Crが６質量％含有されており、残部はＣであった。
A 50 × 50 × 10 mm plate test piece (JIS-SKD61) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and further washed with warm water. This is referred to as Invention Example 3.
The plate-like test piece of Invention Example 3 was cut and the cross section was observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 6 μm was formed on the surface of the plate-shaped test piece.
Next, when the components of the composite carbide layer were analyzed, V was 62 mass%, Ti was 12 mass%, Cr was 6 mass%, and the balance was C.
さらに、複合炭化物層の表面にてＸ線回折を行なった。得られた回折線は、ＶＣの回折線と良く一致していた。
以上の結果から、CrとTiを含有するＶＣからなる複合炭化物層が形成されたと考えられる。
＜実施例４＞
実施例１と同様にして硼砂を溶融させ、1000℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を、浴全体の質量（硼砂と酸化物粉末と還元剤とクロム粉末の合計）に対して10質量％添加し、さらにNb2Ｏ5 粉末を浴全体の質量に対して10質量％，還元剤として粒状のAl粉末を浴全体の質量に対して５質量％を添加した後、クロム粉末を浴全体の質量に対して４質量％を添加して溶融塩浴を準備した。
Further, X-ray diffraction was performed on the surface of the composite carbide layer. The obtained diffraction lines were in good agreement with the VC diffraction lines.
From the above results, it is considered that a composite carbide layer made of VC containing Cr and Ti was formed.
<Example 4>
Borax was melted in the same manner as in Example 1 to prepare a 1000 ° C. bath. In this bath, flaky V 2 O 5 powder is added in an amount of 10% by mass with respect to the total mass of the bath (the total of borax, oxide powder, reducing agent and chromium powder), and Nb 2 O 5 powder is further added to the bath. After adding 10% by mass to the total mass and 5% by mass of granular Al powder as the reducing agent based on the total mass of the bath, add 4% by mass of chromium powder to the total mass of the bath. A molten salt bath was prepared.
この溶融塩浴中に、50×50×10mmの板状試験片（JIS-SKD61）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例４とする。
一方、比較例１として、硼砂を溶融させ、1000℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を浴全体の質量に対して20質量％添加し、さらに還元剤として粒状のAl粉末を浴全体の質量に対して５質量％を添加して溶融塩浴を準備した。この溶融塩浴中に、50×50×10mmの板状試験片（JIS-SKD61）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。
A 50 × 50 × 10 mm plate test piece (JIS-SKD61) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and further washed with warm water. This is referred to as Invention Example 4.
On the other hand, as Comparative Example 1, borax was melted to prepare a 1000 ° C. bath. In this bath, 20% by mass of flaky V 2 O 5 powder is added to the total mass of the bath, and 5% by mass of granular Al powder is added as a reducing agent to the total mass of the bath and melted. A salt bath was prepared. A 50 × 50 × 10 mm plate test piece (JIS-SKD61) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and further washed with warm water.
発明例４と比較例１の板状試験片について、表面の酸化模様の有無を目視で検査したところ、発明例４では酸化模様は認められなかったのに対して、比較例１では酸化模様が発生していた。また、発明例４の表面は銀白色で滑らかであったのに対して、比較例１の表面は黒褐色でザラザラしていた。
次いで、発明例４と比較例１の板状試験片を切断して、その断面を光学顕微鏡で観察した。その結果、いずれの板状試験片の表面に厚さ９μｍの複合炭化物層が形成されていることが確かめられた。
About the plate-shaped test piece of invention example 4 and comparative example 1, when the presence or absence of the oxidation pattern of the surface was visually inspected, in oxidation example 4, the oxidation pattern was not recognized, but in comparative example 1, the oxidation pattern was observed. It has occurred. The surface of Invention Example 4 was silver white and smooth, while the surface of Comparative Example 1 was black brown and rough.
Subsequently, the plate-shaped test pieces of Invention Example 4 and Comparative Example 1 were cut, and the cross sections thereof were observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 9 μm was formed on the surface of any plate-like test piece.
次に、複合炭化物層の成分を分析したところ、発明例４ではＶが61質量％，Nbが16質量％，Crが５質量％含有されており、残部はＣであった。比較例１ではＶが82質量％含有されており、残部はＣであった。
さらに、複合炭化物層の硬さをマイクロビッカース（荷重25grf）で測定した。その結果、発明例４ではHv3660であったのに対して、比較例１ではHv2550であった。
Next, the components of the composite carbide layer were analyzed. In Invention Example 4, V was 61% by mass, Nb was 16% by mass, Cr was 5% by mass, and the balance was C. In Comparative Example 1, 82% by mass of V was contained, and the balance was C.
Further, the hardness of the composite carbide layer was measured with micro Vickers (load 25 grf). As a result, it was Hv3660 in Invention Example 4, whereas it was Hv2550 in Comparative Example 1.
以上の結果から、本発明によれば、表面が滑らかで酸化模様もなく健全な複合炭化物層が形成され、かつその硬さが増加することが分かる。
＜実施例５＞
実施例１と同様にして硼砂を溶融させ、1050℃の浴を作成した。この浴中にFe−Ｖ（JIS-１号フェロバナジウム）粉末を、浴全体の質量（硼砂と合金鋼粉末とクロム粉末の合計）に対して10質量％添加し、さらにFe−Nb合金粉末を浴全体の質量に対して10質量％，クロム粉末を浴全体の質量に対して４質量％を添加して溶融塩浴を準備した。
From the above results, it can be seen that according to the present invention, a healthy composite carbide layer having a smooth surface and no oxidation pattern is formed, and its hardness increases.
<Example 5>
Borax was melted in the same manner as in Example 1 to prepare a bath at 1050 ° C. In this bath, 10 mass% of Fe-V (JIS-1 ferrovanadium) powder is added to the total mass of the bath (the total of borax, alloy steel powder and chromium powder), and Fe-Nb alloy powder is further added. A molten salt bath was prepared by adding 10% by mass with respect to the total mass of the bath and 4% by mass of chromium powder with respect to the total mass of the bath.
この溶融塩浴中に、直径７mm×長さ100mmの丸棒試験片（JIS-SKH51）を５時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例５とする。
一方、比較例２として、硼砂を溶融させ、1050℃の浴を作成した。この浴中にFe−Ｖ粉末を浴全体の質量に対して20質量％添加して溶融塩浴を準備した。この溶融塩浴中に、直径７mm×長さ100mmの丸棒試験片（JIS-SKH51）を５時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。
In this molten salt bath, a round bar test piece (JIS-SKH51) having a diameter of 7 mm and a length of 100 mm was immersed for 5 hours, taken out, air-cooled, and further washed with warm water. This is designated as Invention Example 5.
On the other hand, as Comparative Example 2, borax was melted to prepare a 1050 ° C. bath. A molten salt bath was prepared by adding 20 mass% of Fe-V powder to the total mass of the bath. In this molten salt bath, a round bar test piece (JIS-SKH51) having a diameter of 7 mm and a length of 100 mm was immersed for 5 hours, taken out, air-cooled, and further washed with warm water.
発明例５と比較例２の丸棒試験片を切断して、その断面を光学顕微鏡で観察した。その結果、いずれの丸棒試験片の表面に厚さ８μｍの複合炭化物層が形成されていることが確かめられた。
次に、複合炭化物層の成分を分析したところ、発明例５ではＶが61質量％，Nbが16質量％，Crが５質量％含有されており、残部はＣであった。比較例２ではＶが82質量％含有されており、残部はＣであった。
The round bar specimens of Invention Example 5 and Comparative Example 2 were cut, and the cross sections thereof were observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 8 μm was formed on the surface of any round bar test piece.
Next, the components of the composite carbide layer were analyzed. In Invention Example 5, V was 61% by mass, Nb was 16% by mass, Cr was 5% by mass, and the balance was C. In Comparative Example 2, V was contained by 82% by mass, and the balance was C.
さらに、発明例５と比較例２の丸棒試験片について酸化試験（大気中700℃，１時間）を行ない、酸化増量を測定した。
また比較例３として、表面に複合炭化物層を形成していない直径７mm×長さ100mmの丸棒試験片（JIS-SKH51）についても、酸化試験を行ない、酸化増量を測定した。その結果、発明例５では酸化増量が0.6mg／cm2であったのに対して、比較例２では1.54mg／cm2，比較例３では1.32mg／cm2であった。
Furthermore, the oxidation test (in the atmosphere, 700 ° C., 1 hour) was performed on the round bar test pieces of Invention Example 5 and Comparative Example 2, and the increase in oxidation was measured.
Further, as Comparative Example 3, an oxidation test was conducted on a round bar test piece (JIS-SKH51) having a diameter of 7 mm and a length of 100 mm in which no composite carbide layer was formed on the surface, and the increase in oxidation was measured. As a result, the increase in oxidation in Invention Example 5 was 0.6 mg / cm 2 , whereas in Comparative Example 2, it was 1.54 mg / cm 2 and in Comparative Example 3 was 1.32 mg / cm 2 .
以上の結果から、本発明によれば、耐酸化性に優れた複合炭化物層が形成されることが分かる。
＜実施例６＞
実施例１と同様にして硼砂を溶融させ、1000℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を、浴全体の質量（硼砂と酸化物粉末と還元剤とクロム粉末の合計）に対して10質量％添加し、さらにNb2Ｏ5粉末を浴全体の質量に対して８質量％，還元剤としてＢ4Ｃ粉末を浴全体の質量に対して５質量％を添加した後、クロム粉末を浴全体の質量に対して５質量％を添加して溶融塩浴を準備した。
From the above results, it can be seen that according to the present invention, a composite carbide layer excellent in oxidation resistance is formed.
<Example 6>
Borax was melted in the same manner as in Example 1 to prepare a 1000 ° C. bath. In this bath, flaky V 2 O 5 powder is added in an amount of 10% by mass with respect to the total mass of the bath (the total of borax, oxide powder, reducing agent and chromium powder), and Nb 2 O 5 powder is further added to the bath. After adding 8% by mass to the total mass and 5% by mass of B 4 C powder as a reducing agent based on the total mass of the bath, add 5% by mass of chromium powder to the total mass of the bath. A molten salt bath was prepared.
この溶融塩浴中に、50×50×５mmの板状試験片（JIS-SKD11）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。これを発明例６とする。
一方、比較例４として、硼砂を溶融させ、1000℃の浴を作成した。この浴中に薄片状のＶ2Ｏ5粉末を浴全体の質量に対して20質量％添加し、さらに還元剤としてＢ4Ｃ粉末を浴全体の質量に対して５質量％を添加して溶融塩浴を準備した。この溶融塩浴中に、50×50×５mmの板状試験片（JIS-SKD11）を８時間浸漬した後、取り出して空冷し、さらに温水で洗浄した。
A 50 × 50 × 5 mm plate test piece (JIS-SKD11) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and further washed with warm water. This is designated as Invention Example 6.
On the other hand, as Comparative Example 4, borax was melted to prepare a 1000 ° C. bath. In this bath, 20% by mass of flaky V 2 O 5 powder is added to the total mass of the bath, and 5% by mass of B 4 C powder is added as a reducing agent to the total mass of the bath to melt. A salt bath was prepared. A 50 × 50 × 5 mm plate test piece (JIS-SKD11) was immersed in this molten salt bath for 8 hours, taken out, air-cooled, and further washed with warm water.
発明例６と比較例４の板状試験片を切断して、その断面を光学顕微鏡で観察した。その結果、いずれの板状試験片の表面に厚さ10μｍの複合炭化物層が形成されていることが確かめられた。
次に、複合炭化物層の成分を分析したところ、発明例６ではＶが60質量％，Nbが20質量％，Crが６質量％含有されており、残部はＣであった。比較例４ではＶが80質量％含有されており、残部はＣであった。
The plate-like test pieces of Invention Example 6 and Comparative Example 4 were cut, and the cross section was observed with an optical microscope. As a result, it was confirmed that a composite carbide layer having a thickness of 10 μm was formed on the surface of any plate-like test piece.
Next, the components of the composite carbide layer were analyzed. As a result, in Invention Example 6, V was 60 mass%, Nb was 20 mass%, Cr was 6 mass%, and the balance was C. In Comparative Example 4, V was contained by 80 mass%, and the balance was C.
さらに、複合炭化物層の表面にてＸ線回折を行なった。得られた回折線は、ＶＣの回折線と良く一致していた。
以上の結果から、CrとNbを含有するＶＣからなる複合炭化物層が形成されたと考えられる。
また、比較例５としてイオン窒化処理した板状試験片（JIS-SKD11），比較例６として化学的蒸着法（いわゆるＣＶＤ法）によってTiＣ被覆した板状試験片（JIS-SKD11）を作成した。
Further, X-ray diffraction was performed on the surface of the composite carbide layer. The obtained diffraction lines were in good agreement with the VC diffraction lines.
From the above results, it is considered that a composite carbide layer made of VC containing Cr and Nb was formed.
Further, a plate-like test piece (JIS-SKD11) subjected to ion nitriding treatment as Comparative Example 5 and a plate-like test piece (JIS-SKD11) coated with TiC by a chemical vapor deposition method (so-called CVD method) were prepared as Comparative Example 6.
発明例６と比較例４，５，６の板状試験片について、それぞれ摩擦試験（大越式迅速摩擦試験機，相手材：S45C調質材，摩擦速度：2.28ｍ／秒，摩擦距離：100ｍ，潤滑なし）を行ない、摩耗量を測定した。その結果、発明例６では摩耗量が28×10-3 mm3であったのに対して、比較例４では43×10-3 mm3，比較例５では1086×10-3 mm3，比較例６では56×10-3 mm3であった。 For the plate-like specimens of Invention Example 6 and Comparative Examples 4, 5, and 6, friction tests (Ogoshi rapid friction test machine, mating material: S45C tempered material, friction speed: 2.28 m / sec, friction distance: 100 m, The amount of wear was measured. As a result, the amount of wear in Invention Example 6 was 28 × 10 −3 mm 3 , while that in Comparative Example 4 was 43 × 10 −3 mm 3 , and Comparative Example 5 was 1086 × 10 −3 mm 3 . In Example 6, it was 56 × 10 −3 mm 3 .
以上の結果から、本発明によれば、耐摩耗性に優れた複合炭化物層が形成されることが分かる。 From the above results, it can be seen that according to the present invention, a composite carbide layer having excellent wear resistance is formed.
Claims (8)
(a)Ti、Ｖ、NbおよびTaの中から選ばれる２種以上の金属元素を含む金属粉末
(b)Crを含むクロム粉末
(c)硼砂 A composite carbide layer containing chromium on the surface of the member by immersing a member having a predetermined shape in a molten salt bath made of the powder of the following groups (a), (b) and (c): Forming a surface covering member.
(a) Metal powder containing two or more metal elements selected from Ti, V, Nb and Ta
(b) Cr powder containing Cr
(c) Borax
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007025048A JP4855961B2 (en) | 2007-02-05 | 2007-02-05 | Surface covering member and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007025048A JP4855961B2 (en) | 2007-02-05 | 2007-02-05 | Surface covering member and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008189988A true JP2008189988A (en) | 2008-08-21 |
| JP4855961B2 JP4855961B2 (en) | 2012-01-18 |
Family
ID=39750356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007025048A Expired - Fee Related JP4855961B2 (en) | 2007-02-05 | 2007-02-05 | Surface covering member and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4855961B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011028032A2 (en) * | 2009-09-04 | 2011-03-10 | Koong Shin | Chromizing solution and method of manufacturing special steel using chromizing |
| JP2012031480A (en) * | 2010-07-30 | 2012-02-16 | Daito Kogyo Kk | Surface treatment method for iron alloy material |
| CN102383134A (en) * | 2010-08-27 | 2012-03-21 | 上海明嘉金属科技有限公司 | Method for surface strengthening treatment of automobile forming precision die |
| CN105239037A (en) * | 2015-11-02 | 2016-01-13 | 杭州持正科技股份有限公司 | Chain pin shaft surface vanadinizing strengthening process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110230025A (en) * | 2019-06-13 | 2019-09-13 | 武汉理工大学 | A kind of preparation method of aluminium alloy casting die composite coating |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5358440A (en) * | 1976-11-08 | 1978-05-26 | Toyoda Chuo Kenkyusho Kk | Method of forming composite carbide layer of titanium and chromium on surface of ferrous alloy containing carbon |
| JPS57207166A (en) * | 1981-06-01 | 1982-12-18 | Hitachi Metals Ltd | Surface treatment |
| JPS61291962A (en) * | 1985-06-17 | 1986-12-22 | Toyota Central Res & Dev Lab Inc | Surface treatment of iron alloy material |
| JPH10110253A (en) * | 1996-10-04 | 1998-04-28 | Tocalo Co Ltd | Conductor roll for electroplating and its production |
| JP2002332562A (en) * | 2001-05-10 | 2002-11-22 | Sogi Kogyo Kk | Method for producing heat resistant member applicable for exhaust guide assembly of vgs type turbocharger |
-
2007
- 2007-02-05 JP JP2007025048A patent/JP4855961B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5358440A (en) * | 1976-11-08 | 1978-05-26 | Toyoda Chuo Kenkyusho Kk | Method of forming composite carbide layer of titanium and chromium on surface of ferrous alloy containing carbon |
| JPS57207166A (en) * | 1981-06-01 | 1982-12-18 | Hitachi Metals Ltd | Surface treatment |
| JPS61291962A (en) * | 1985-06-17 | 1986-12-22 | Toyota Central Res & Dev Lab Inc | Surface treatment of iron alloy material |
| JPH10110253A (en) * | 1996-10-04 | 1998-04-28 | Tocalo Co Ltd | Conductor roll for electroplating and its production |
| JP2002332562A (en) * | 2001-05-10 | 2002-11-22 | Sogi Kogyo Kk | Method for producing heat resistant member applicable for exhaust guide assembly of vgs type turbocharger |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011028032A2 (en) * | 2009-09-04 | 2011-03-10 | Koong Shin | Chromizing solution and method of manufacturing special steel using chromizing |
| WO2011028032A3 (en) * | 2009-09-04 | 2011-06-30 | Koong Shin | Chromizing solution and method of manufacturing special steel using chromizing |
| KR101135007B1 (en) | 2009-09-04 | 2012-04-19 | 신진우 | The solution for the chromium diffusion and the manufacturing method of the the chromium diffusion layer |
| JP2012031480A (en) * | 2010-07-30 | 2012-02-16 | Daito Kogyo Kk | Surface treatment method for iron alloy material |
| CN102383134A (en) * | 2010-08-27 | 2012-03-21 | 上海明嘉金属科技有限公司 | Method for surface strengthening treatment of automobile forming precision die |
| CN105239037A (en) * | 2015-11-02 | 2016-01-13 | 杭州持正科技股份有限公司 | Chain pin shaft surface vanadinizing strengthening process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4855961B2 (en) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Birol | High temperature sliding wear behaviour of Inconel 617 and Stellite 6 alloys | |
| JP4855961B2 (en) | Surface covering member and manufacturing method thereof | |
| Liu et al. | Microstructure and properties of AlCoCrFeNiTi high-entropy alloy coating on AISI1045 steel fabricated by laser cladding | |
| CN110249065A (en) | The manufacturing method of free-cutting machinability copper alloy and free-cutting machinability copper alloy | |
| JP2012031480A (en) | Surface treatment method for iron alloy material | |
| Sim et al. | Microstructure, mechanical properties, corrosion and wear behavior of high-entropy alloy AlCoCrFeNix (x> 0 the) and medium-entropy alloy (x= 0) | |
| CN105026530A (en) | Coating for high temperature applications with tribological stress | |
| JP5867332B2 (en) | Aluminum alloy wear-resistant member and method for producing the same | |
| DE102006011384A1 (en) | Roll for metalworking, in particular continuous casting roll, and method for producing such a roll | |
| JP4844874B2 (en) | Manufacturing method of press-molded products | |
| Mertgenc et al. | The wear and microstructural characterization of copper surface coated with TiC reinforced FeAl intermetallic composite by ESD method | |
| JP2003531727A (en) | Mold walls of continuous casting molds for steel, especially wide side walls | |
| JP2011504147A (en) | Objects with a ductile and corrosion-resistant surface layer | |
| CA2891886C (en) | Hard coating having excellent adhesion resistance to soft metal | |
| Natarajan et al. | Development of numerical model for predicting the characteristics of Ni–SiC nano composite coatings on AISI 1022 substrate | |
| Güler et al. | The effect of advanced electrodeposited Ni-P-Cu coatings obtained with scrap cu plates on the tribological performance of Al powder metallurgy products | |
| KR100740899B1 (en) | Mold wall, especially a broadside wall of a continuous casting mold for steel | |
| Zhao et al. | Effects of the Environment and Temperature on the Tribological Behavior of TiZrHfNbTa Refractory High-Entropy Alloy | |
| US20160046100A1 (en) | Object having a ductile and corrosion resistant surface layer | |
| Othman et al. | Effect of current density and fly ash composition on nickel grain size and hardness of nickel-fly ash composite coating deposited on aluminum alloy 6061 | |
| CN115404376B (en) | High-strength abrasion-resistant multi-element copper alloy and application thereof | |
| Harmukh et al. | Effect of CNT-Ni-P composite coating on tribological behaviour for brake pad system | |
| JP2012219365A (en) | Manufacturing method of metallic material for plastic woking and worked metal product | |
| JP2012519781A (en) | Lead-free brass alloy | |
| JP4773486B2 (en) | Surface treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090825 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110929 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111025 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111027 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141104 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4855961 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |