JPH0665710A - Formation of thermally spraying carbide film - Google Patents
Formation of thermally spraying carbide filmInfo
- Publication number
- JPH0665710A JPH0665710A JP4226203A JP22620392A JPH0665710A JP H0665710 A JPH0665710 A JP H0665710A JP 4226203 A JP4226203 A JP 4226203A JP 22620392 A JP22620392 A JP 22620392A JP H0665710 A JPH0665710 A JP H0665710A
- Authority
- JP
- Japan
- Prior art keywords
- carbide
- carbon
- thermal spray
- sprayed
- thermal
- 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
Landscapes
- Coating By Spraying Or Casting (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、各種耐摩耗部材（例え
ば、ロール，ポンプのロータなど）の製造に際して、部
材表面への硬質炭化物の溶射膜の形成方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a sprayed film of hard carbide on the surface of a wear-resistant member (for example, a roll or a rotor of a pump) when manufacturing the wear-resistant member.
【０００２】[0002]
【従来の技術】従来から、各種耐摩耗部材の製造に際し
て、部材表面に炭化物と結合金属との溶射膜を形成する
ことは広く知られており、さらに、溶射膜を熱間等方加
圧処理（ＨＩＰ）により緻密化することも、例えば、特
開昭６１−１５９５６６号公報、特開平３−７９７５１
号公報等に記載されている。2. Description of the Related Art Conventionally, it has been widely known to form a sprayed film of carbide and a bond metal on the surface of various wear resistant members, and further, the sprayed film is subjected to hot isostatic pressing. Densification by (HIP) is also possible, for example, in Japanese Patent Laid-Open No. 61-159566 and Japanese Patent Laid-Open No. 3-79571.
It is described in Japanese Patent Publication No.
【０００３】また、特開平４−１０３７５０号公報に
は、Ｓｉ＋Ｂ＋Ｃ成分を含有させ、窒化物、硼化物、炭
化物を合成させて、硬化、強化させることが記載されて
いる。Further, Japanese Patent Application Laid-Open No. 4-103750 discloses that Si + B + C components are contained and nitrides, borides and carbides are synthesized, and then hardened and strengthened.
【０００４】[0004]
【発明が解決しようとする課題】かかる炭化物と結合金
属からなる溶射材をプラズマ炎のような高熱で溶融し、
溶射するに際しては、大気中の酸素により溶射材中の炭
素がＣＯ，ＣＯ2 となり、材料中の炭素量が減少する傾
向がある。The thermal spray material composed of such a carbide and a binding metal is melted by high heat such as plasma flame,
At the time of thermal spraying, carbon in the thermal spray material becomes CO and CO 2 due to oxygen in the atmosphere, and the amount of carbon in the material tends to decrease.
【０００５】脱炭量は、大気プラズマ溶射が最も多く、
減圧プラズマ溶射や高速炎溶射では少なくなるなど溶射
の方法により異なるが、いずれの溶射方法でも炭素量が
減少する傾向は同じである。The amount of decarburization is highest in atmospheric plasma spraying,
Although it depends on the method of thermal spraying, such as decreasing with reduced pressure plasma spraying or high-speed flame spraying, the tendency for the amount of carbon to decrease is the same regardless of the thermal spraying method.
【０００６】溶射材中の炭素が減少すると、図１のＷ−
Ｃｏ−Ｃ系の状態図に示されているように、Ｃｏ3 Ｗ3
Ｃ，Ｃｏ6 Ｗ6 Ｃ，Ｃｏ2 Ｗ4 Ｃのような結合金属との
複炭化物が形成される。この複炭化物は、溶射時にも形
成されるが、溶射後の結合強化や強度向上のための熱処
理によって、溶射直後の非平衡状態から平衡状態への変
態の進行によって多く形成され、材料の特性が劣化した
ものとなる。When the carbon content in the thermal spray material is reduced, W- in FIG.
As shown in the phase diagram of the Co-C system, Co 3 W 3
Double carbides with a binding metal such as C, Co 6 W 6 C, Co 2 W 4 C are formed. This double carbide is also formed during thermal spraying, but it is often formed by the progress of transformation from the non-equilibrium state to the equilibrium state immediately after thermal spraying by the heat treatment for strengthening the bond and improving the strength after thermal spraying, and the material characteristics are It becomes deteriorated.
【０００７】この種の炭化物の形成は、結合金属の減少
により高温での塑性変形が起こりにくくなり、熱間等方
加圧処理による緻密化に際し、処理温度が高くなった
り、気孔が残留し易くなる。The formation of this kind of carbide makes it difficult for plastic deformation to occur at high temperatures due to the decrease in the amount of binding metal, and when the densification is performed by hot isostatic pressing, the processing temperature becomes high and pores are likely to remain. Become.
【０００８】この複炭化物の形成は、溶射膜の靱性を高
めるべき結合金属が硬くて脆い炭化物となり、溶射膜の
強度と靱性の低下を招く。このため、溶射後の加工が困
難となる。The formation of this double carbide causes the binding metal, which should enhance the toughness of the sprayed coating, to become a hard and brittle carbide, resulting in a decrease in the strength and toughness of the sprayed coating. Therefore, the processing after the thermal spraying becomes difficult.
【０００９】また、この複炭化物は、アルカリに極めて
溶解しやすく、アルカリ雰囲気中での耐食性が極端に低
下する。Further, this double carbide is very easily dissolved in alkali, and the corrosion resistance in an alkali atmosphere is extremely lowered.
【００１０】さらに、炭素量が少ない場合には、例えば
ＷＣ−Ｃｏ系ではＷＣの分解によるＷの析出が起こる。
Ｗは、金属中でも最も熱膨張率が小さく、台金と溶射膜
の熱膨張率の差による残留応力の形成が大きくなり、溶
射膜の強度低下を来す。Further, when the amount of carbon is small, for example, in the WC-Co system, W is precipitated by the decomposition of WC.
W has the smallest coefficient of thermal expansion among metals, and the residual stress is increased due to the difference in coefficient of thermal expansion between the base metal and the sprayed film, resulting in a decrease in strength of the sprayed film.
【００１１】また、母材と溶射膜の熱膨張率の差による
残留応力を緩和するために、母材側では硬質粒子を少な
くして結合金属を多くし、表面側では硬さを増すために
硬質粒子を多くし、結合金属を少なくする方法がよく採
られ、熱間等方加圧処理した緻密な被膜を形成するに際
して有効な手段である。In order to reduce the residual stress due to the difference in the coefficient of thermal expansion between the base material and the sprayed coating, hard particles are reduced on the base material side to increase the binding metal, and hardness on the surface side is increased. A method of increasing the amount of hard particles and decreasing the amount of bound metal is often adopted, and is an effective means for forming a dense coating film subjected to hot isostatic pressing.
【００１２】しかし、溶射時に脱炭すると、熱間等方加
圧処理時に結合金属は複炭化物を形成し、残留応力緩和
の効果を著しく損なう。However, if decarburization is performed during thermal spraying, the binding metal forms double carbide during hot isostatic pressing, and the effect of relaxing residual stress is significantly impaired.
【００１３】また、溶射膜中の炭素量が減少すると、前
述した複炭化物の形成のほか、炭化物の金属／炭素比が
大きい炭化物が形成されることがある。たとえば、Ｃｒ
3 Ｃ2 がＣｒ7 Ｃ3 となる変化である。このとき、炭化
物の熱膨張率は１１．７×１０-6／℃から９．４×１０
-6／℃に減少し、鋼を母材とする溶射膜の形成に、とく
に溶射後に熱処理を伴う場合には、熱膨張差による残留
応力が大きくなり、不利となる。Further, when the amount of carbon in the sprayed coating decreases, in addition to the formation of the above-mentioned double carbide, a carbide having a large metal / carbon ratio of carbide may be formed. For example, Cr
This is a change in which 3 C 2 becomes Cr 7 C 3 . At this time, the coefficient of thermal expansion of the carbide was 11.7 × 10 −6 / ° C. to 9.4 × 10 6.
-6 / ° C, which is disadvantageous because the residual stress due to the difference in thermal expansion increases when forming a sprayed film using steel as a base material, especially when heat treatment is performed after spraying.
【００１４】このような変態に伴う不都合も、溶射材中
に炭素分を添加配合するか、溶射後の溶射体に添加配合
することで、所定の炭化物と結合金属からなる溶射体と
し、解決することができる。The inconvenience associated with such transformation is solved by adding and blending carbon content in the thermal spray material or by adding and blending it in the thermal sprayed body after thermal spraying to obtain a thermal sprayed body composed of a predetermined carbide and a binding metal. be able to.
【００１５】本発明において解決すべき課題は、金属、
セラミックス基体上に炭化物と結合金属からなる溶射材
を溶射して硬質皮膜を形成するに当たって、炭化物の分
解脱炭および結合金属との複炭化物形成による特性の劣
化を防止するための手段を提供することにある。The problems to be solved in the present invention are metal,
To provide means for preventing degradation of characteristics due to decomposition and decarburization of carbides and formation of double carbides with a bond metal in forming a hard coating by spraying a thermal spray material composed of a carbide and a bond metal on a ceramic substrate. It is in.
【００１６】[0016]
【課題を解決するための手段】第１の発明は、IV、Ｖ、
VI族金属の炭化物と結合金属からなる溶射材の溶射に際
して、溶射材中に、炭化物の脱炭量に見合う分だけ炭素
分を添加配合することを特徴とする。[Means for Solving the Problems] The first invention is IV, V,
When thermal spraying a thermal spray material composed of a carbide of a Group VI metal and a bond metal, carbon is added to the thermal spray material in an amount corresponding to the decarburization amount of the carbide.
【００１７】また、第２の発明は、IV、Ｖ、VI族金属の
炭化物と結合金属からなる溶射膜に、溶射膜を形成する
炭化物の脱炭量に見合う分だけ炭素分を添加配合するこ
とを特徴とする。A second aspect of the present invention is to add a carbon content to a thermal spray coating composed of carbides of group IV, V and VI metals and a bonding metal in an amount corresponding to the decarburization amount of the carbide forming the thermal spray coating. Is characterized by.
【００１８】また、第３の発明は、IV、Ｖ、VI族金属の
炭化物と結合金属からなる溶射材を溶射し、さらにこの
溶射膜に熱処理を加える場合において、溶射材の溶射に
際して溶射材中にあるいは溶射膜の熱処理に際して溶射
膜中に、炭化物の脱炭量に見合うだけ炭素分を添加配合
することを特徴とする。A third aspect of the present invention is that, when a thermal spray material composed of carbides of group IV, V, and VI metals and a bond metal is sprayed and a heat treatment is applied to the spray coating, the spray material is sprayed during the thermal spraying. Alternatively, or in the heat treatment of the thermal spray coating, the carbon content is added to the thermal spray coating in an amount corresponding to the decarburization amount of the carbide.
【００１９】結合金属としては、通常炭化物の結合材と
して用いられているＦｅ、Ｃｏ、Ｎｉ、Ｎｉ−Ｃｒ等の
鉄族金属あるいは、その合金を任意用いることができ
る。As the binding metal, an iron group metal such as Fe, Co, Ni or Ni-Cr which is usually used as a binding material for carbide, or an alloy thereof can be arbitrarily used.
【００２０】添加配合する炭素の配合量としては、溶射
後の複炭化物の発生量が問題にならない程度の炭素量と
し、好ましくは、所定の炭化物と結合金属の相となるよ
うに炭素量を調整する。The amount of carbon to be added and blended is such that the amount of double carbide generated after thermal spraying does not matter, and preferably the amount of carbon is adjusted so as to form a predetermined carbide and bond metal phase. To do.
【００２１】添加する炭素としては、粉砕黒鉛，球晶黒
鉛，カーボンブラック等を使用できるが、とくに、酸化
し難い黒鉛粉末を使用するのがよい。As carbon to be added, crushed graphite, spherulite graphite, carbon black or the like can be used, but it is particularly preferable to use graphite powder which is difficult to oxidize.
【００２２】また、添加配合する炭素は、黒鉛粉末と結
合金属をメカノフュージョンによって混合して得た黒鉛
粉末表面に結合金属の被覆層を形成した粒子を用いるこ
とができる。Further, as the carbon to be added and blended, particles having a coating layer of a binding metal formed on the surface of the graphite powder obtained by mixing graphite powder and a binding metal by mechanofusion can be used.
【００２３】[0023]
【作用】本発明は、溶射材中に炭素を含有せしめること
によって、雰囲気を炭化雰囲気とし、溶射中、炭化物中
の炭素の消耗を防止することができ、あるいは形成され
た溶射膜の熱処理時に、復炭することが可能となる。The present invention makes it possible to prevent carbon from being consumed in the carbide during the thermal spraying by making the thermal spraying material contain carbon, thereby making it possible to prevent the carbon from being consumed in the thermal spraying. It is possible to recover coal.
【００２４】[0024]
実施例ｌ 軟鋼からなる基体上に、ＷＣ−Ｃｏ系の溶射材の溶射膜
を形成するに当たって、本発明を適用した例について説
明する。Example 1 An example in which the present invention is applied in forming a sprayed film of a WC-Co based spraying material on a base made of mild steel will be described.
【００２５】粒子径が１０ミクロンのＷＣ粉末８３重量
％と、２ミクロン径のＣｏ粉末１７重量％とからなる混
合粉末を、大気プラズマ溶射装置で溶射電流値８００ア
ンペア、アークガスにＡｒを使用した条件で、２ｍｍ厚
に溶射膜を形成し、１１００℃で保持時問ｌ時間、Ａｒ
ガス雰囲気の条件で熱処理を行った。この溶射膜をＸ線
回折により相の同定をすると、Ｃｏ6 Ｗ6 ＣとＷＣの２
相を主とし、さらにＣｏ2 Ｗ4 Ｃ，Ｗの相が検出され
た。この溶射膜の炭素量は、溶射材の状態で５．１重量
％であったものが溶射膜では２．９重量％であり、溶射
時の脱炭量は２．２重量％であった。また、熱処理によ
る脱炭量はほとんどなかった。Conditions in which a mixed powder consisting of 83% by weight of WC powder having a particle diameter of 10 microns and 17% by weight of Co powder having a diameter of 2 microns was sprayed with an atmospheric plasma spraying apparatus at a current value of 800 amps and an arc gas of Ar. To form a sprayed film with a thickness of 2 mm and hold it at 1100 ° C for 1 hour.
The heat treatment was performed under the condition of gas atmosphere. When the phases of this sprayed film were identified by X-ray diffraction, two phases of Co 6 W 6 C and WC were obtained.
A phase was mainly detected, and a Co 2 W 4 C, W phase was detected. The carbon content of this sprayed film was 5.1% by weight in the state of the sprayed material, but was 2.9% by weight in the sprayed film, and the decarburization amount at the time of spraying was 2.2% by weight. Moreover, the amount of decarburization due to the heat treatment was scarce.
【００２６】この結果に基づいて、上記組成を有するＷ
ＣとＣｏとの粉末に、粒子径が８ミクロンの黒鉛を加
え、ボールミルでｌ時間の条件で混合し、上記の条件で
溶射、熱処理を行った。混合物の組成は、ＷＣ７９．３
重量％、Ｃｏ１６．３重量％、黒鉛４．４重量％であっ
て、ＷＣとＣｏの所定組成の重量比が８３：１７の上記
溶射材９５．６重量％に対して、炭素量が４．４重量％
多いものであった。Based on this result, W having the above composition
Graphite having a particle size of 8 microns was added to the powders of C and Co, mixed for 1 hour in a ball mill, and sprayed and heat-treated under the above conditions. The composition of the mixture is WC79.3.
% By weight, Co 16.3% by weight, graphite 4.4% by weight, and the amount of carbon is 4. 5% by weight with respect to 95.6% by weight of the thermal spray material having a predetermined compositional ratio of WC and Co of 83:17. 4% by weight
There were many.
【００２７】この溶射材を、上記の黒鉛を余分に加えな
い溶射材と同様の条件で軟鋼に溶射したところ、溶射膜
の炭素量が５．ｌ重量％となり、さらに上記と同じ条件
で熱処理したところ、ＷＣとＣｏの２相からなる優良な
溶射膜を得ることができた。When this thermal spray material was sprayed on mild steel under the same conditions as the above-mentioned spray material without the addition of graphite, the carbon content of the spray coating was 5. When the heat treatment was carried out under the same conditions as above, a good thermal spray coating consisting of two phases of WC and Co could be obtained.
【００２８】実施例２ 実施例ｌで述べた２種の溶射材を実施例ｌと同じ条件で
溶射して試料を作成した。この２試料を温度１１００℃
で熱間等方加圧処理を施した。試片は軟鋼の缶に封入
し、圧力媒体としてＡｒガスを用い、圧力はｌ００ＭＰ
ａ、保持時間は１時問の条件とした。この結果、Ｃｏ6
Ｗ6 ＣとＷＣの２相を主とする試料は気孔が残留し完全
に緻密化せず、ＷＣとＣｏの２相からなる溶射膜のみが
完全に緻密化した。溶射膜の炭素量を調整するとこで、
低い温度で熱問等方加圧処理により緻密化することがで
きた。Example 2 A sample was prepared by spraying the two types of thermal spraying materials described in Example 1 under the same conditions as in Example 1. The temperature of these two samples is 1100 ° C
Was subjected to hot isostatic pressing. The test piece was enclosed in a mild steel can, Ar gas was used as the pressure medium, and the pressure was 100MP.
a, the holding time was set to 1 hour. As a result, Co 6
The sample mainly composed of the two phases of W 6 C and WC did not completely densify due to the remaining pores, and only the thermal spray coating composed of the two phases of WC and Co completely densified. By adjusting the carbon content of the sprayed film,
It was possible to densify by the hot isostatic pressing treatment at a low temperature.
【００２９】熱間等方加圧処理の温度を１２００℃とす
ると、２種の試料ともに完全に緻密化した。この試料に
ついて圧痕法により破壊靱性値の測定をしたところ、炭
素量を調整しない試料では８ＭＰａ（ｍ）0.5 、調整し
た試料では２０ＭＰａ（ｍ）0.5 となった。溶射膜の炭
素量を調整した上で熱間等方加圧処理することにより、
靱性の高い優良な溶射膜を形成することができた。When the temperature of the hot isostatic pressing treatment was 1200 ° C., the two samples were completely densified. This was a measure of fracture toughness by indentation method for samples, 8 MPa in samples without adjusting the amount of carbon (m) 0.5, the adjusted sample became 20MPa (m) 0.5. By adjusting the carbon content of the sprayed film and then subjecting it to hot isostatic pressing,
It was possible to form an excellent sprayed coating having high toughness.
【００３０】実施例３ 実施例ｌの黒鉛粉末を単純にＷＣ粉末とＣo 粉末に加え
た溶射材を用い、同じ条件で溶射して１０個の試片を作
成し、溶射膜の炭素量を測定したところ、4.９重量％か
ら５．３重量％の範囲でばらついた。Example 3 Using a thermal spray material obtained by simply adding the graphite powder of Example 1 to WC powder and Co powder, 10 samples were prepared by thermal spraying under the same conditions, and the carbon content of the sprayed film was measured. As a result, there was variation in the range of 4.9% by weight to 5.3% by weight.
【００３１】そこで、８ミクロンの黒鉛粉末２１．３重
量％と２ミクロンのＣｏ粉末７８．７重量％をメカノフ
ュージョンで混合して、黒鉛粉末粒子の表面にＣｏ粉末
粒子が分散したＣ−Ｃｏメカノフュージョン粉末を調製
した。Then, 21.3% by weight of 8 micron graphite powder and 78.7% by weight of 2 micron Co powder were mixed by mechanofusion, and a C-Co mechanograph in which Co powder particles were dispersed on the surface of the graphite powder particles. A fusion powder was prepared.
【００３２】この粉末２０．７重量％とＷＣ粉末７９．
３重量％（ＷＣ：Ｃｏ：Ｃが重量比で７９．３：１６．
３：４．４となる）に配合して、ボールミル混合し溶射
材とした。20.7% by weight of this powder and 79.
3 wt% (WC: Co: C in a weight ratio of 79.3: 16.
3: 4.4) and mixed in a ball mill to obtain a thermal spray material.
【００３３】この溶射材を、実施例ｌと同様の条件で軟
鋼に溶射したところ、溶射膜の炭素量が５．８重量％と
なり、さらに上記と同じ条件で熱処理したところ、ＷＣ
とＣｏの２相に遊離黒鉛が生じた溶射膜ができた。When this sprayed material was sprayed on mild steel under the same conditions as in Example 1, the carbon content of the sprayed film was 5.8% by weight. Further, when heat-treated under the same conditions as above, WC
A sprayed film having free graphite in the two phases of Co and Co was formed.
【００３４】つぎに、８ミクロンの黒鉛粉末１６．３重
量％と２ミクロンのＣｏ粉末８３．７重量％をメカノフ
ュージョンで混合して、黒鉛粉末粒子の表面にＣｏ粉末
粒子が分散したＣ−Ｃｏメカノフュージョン粉末を調整
した。Next, 16.3% by weight of 8 micron graphite powder and 83.7% by weight of 2 micron Co powder were mixed by mechanofusion, and C-Co in which Co powder particles were dispersed on the surface of the graphite powder particles. A mechanofusion powder was prepared.
【００３５】この粉末１９．７重量％とＷＣ粉末８０．
３重量％（ＷＣ：Ｃｏ：Ｃが重量比で８０．３：１６．
４：３．３となる）に配合して、ボールミル混合し溶射
材とした。19.7% by weight of this powder and 80.
3 wt% (WC: Co: C in a weight ratio of 80.3: 16.
4: 3.3) and mixed with a ball mill to obtain a thermal spray material.
【００３６】この溶射材を、上記の黒鉛を余分に加えな
い溶射材と同様の条件で軟鋼に溶射したところ、溶射膜
の炭素量が５．ｌ重量％となり、さらに上記と同じ条件
で熱処理したところ、ＷＣとＣｏの２相からなる優良な
溶射膜を得ることができた。When this thermal spray material was sprayed on mild steel under the same conditions as those for the above-mentioned spray material without the addition of graphite, the carbon content of the sprayed film was 5. When the heat treatment was carried out under the same conditions as above, a good thermal spray coating consisting of two phases of WC and Co could be obtained.
【００３７】この溶射材を用い、同じ条件で溶射して１
０個の試片を作成し、溶射膜の炭素量を測定したとこ
ろ、５．０５重量％から５．１５重量％の間でばらつ
き、いずれの試片も熱処理後、ＷＣとＣｏの２相の溶射
膜とすることができた。Using this thermal spray material, thermal spraying was carried out under the same conditions.
When 0 samples were prepared and the carbon content of the sprayed film was measured, it varied between 5.05% by weight and 5.15% by weight, and all of the samples had two phases of WC and Co after heat treatment. It could be a sprayed film.
【００３８】黒鉛粉末をＷＣとＣｏに単純に混合するよ
りも、黒鉛とＣｏをあらかじめメカノフュージョンによ
り黒鉛の周囲にＣｏが被覆した粉末を調整した方が、溶
射時の脱炭量が小さくかつ安定的となり、溶射、熱処理
後にＷＣとＣｏの２相組織とすることが容易になった。Rather than simply mixing graphite powder with WC and Co, it is better to prepare a powder in which Co is coated around graphite and Co by mechanofusion in advance, so that the decarburization amount during spraying is small and stable. It became easy to form a two-phase structure of WC and Co after thermal spraying and heat treatment.
【００３９】実施例４ 溶射後の形成された溶射膜の復炭に係る第２の発明の実
施例である。Embodiment 4 It is an embodiment of the second invention relating to the recarburization of the sprayed film formed after the spraying.
【００４０】実施例ｌの黒鉛を加えない溶射材を用い、
同様の条件で溶射し、２ｍｍ厚の溶射膜を形成した。こ
の試料に熱間等圧加圧処理を施した。試料は、処理に先
立ち軟鋼缶に封入を行った。Using the thermal spray material of Example l containing no graphite,
Thermal spraying was performed under the same conditions to form a sprayed film having a thickness of 2 mm. This sample was subjected to hot isostatic pressing. Samples were encapsulated in mild steel cans prior to processing.
【００４１】軟鋼の缶に封入する際に、缶と試料の間に
１．黒鉛粉末、２．黒鉛フェルトを充填した。また、
３．軟鋼の缶の内壁と溶射膜の双方に黒鉛を分散した塗
料を塗布、乾燥したのち、封入した試料も作成した。比
較試料として、４．軟鋼缶にそのまま溶射試料を封入し
た試料も作成した。When encapsulating in a mild steel can, 1. Graphite powder, 2. Filled with graphite felt. Also,
3. A paint in which graphite was dispersed was applied to both the inner wall of the mild steel can and the thermal spray coating, dried, and then a sealed sample was also prepared. As a comparative sample, 4. A sample was also prepared in which a thermal spray sample was enclosed as it was in a mild steel can.
【００４２】これらの試料を温度と保持時間を変えて、
ｌ００ＭＰａ、Ａｒガス中で熱間等方加圧処理した。処
理後の試料を切り出し光学顕微鏡で観察したところ、溶
射膜の表面が炭化し、ＷＣとＣｏの２相組織となってい
た。熱間等方加圧処理の条件と表面の炭化した層の厚さ
の関係を表ｌに示す。このように、浸炭雰囲気中で熱処
理することで、溶射材に黒鉛を加えるのと同様に、溶射
膜中の炭素量を増加し、ＷＣとＣｏの２相からなる優良
な溶射膜を形成することができた。軟鋼缶にそのまま封
入した試料は、炭化によるＷＣとＣｏの２相組織が形成
されなかったばかりでなく、溶射膜と軟鋼缶が反応し溶
射膜が破壊した。By changing the temperature and holding time of these samples,
Hot isostatic pressing was performed in Ar gas at 100 MPa. When the sample after the treatment was cut out and observed with an optical microscope, the surface of the sprayed film was carbonized and a two-phase structure of WC and Co was formed. Table 1 shows the relationship between the conditions of hot isostatic pressing and the thickness of the carbonized layer on the surface. In this way, by performing heat treatment in a carburizing atmosphere, the amount of carbon in the sprayed film is increased and a good sprayed film composed of two phases of WC and Co is formed, as in the case of adding graphite to the sprayed material. I was able to. In the sample directly enclosed in the mild steel can, not only the two-phase structure of WC and Co was not formed due to carbonization, but also the thermal spray coating and the mild steel can reacted and the thermal spray coating was destroyed.
【００４３】[0043]
【表１】 実施例５ 軟鋼からなる基体上に、Ｃｒ3 Ｃ2 −Ｎｉ系の溶射材の
溶射膜を形成するに当たって、本発明を適用した例につ
いて説明する。[Table 1] Example 5 An example in which the present invention is applied in forming a sprayed film of a Cr 3 C 2 —Ni-based spraying material on a base made of mild steel will be described.
【００４４】粒子径が１０ミクロンのＣｒ3 Ｃ2 粉末７
５重量％と、２ミクロン径のＮｉ−Ｃｒ合金（Ｎｉ／Ｃ
ｒの重量比＝８０／２０）粉末２５重量％とからなる混
合粉末を、大気プラズマ溶射装置で溶射電流値８００ア
ンペア、アークガスにＡｒを使用した条件で、２ｍｍ厚
に溶射膜を形成し、１１００℃で保持時間１時間、Ａｒ
ガス雰囲気の条件で熱処理を行った。この溶射膜をＸ線
回折により相の同定をするとＣｒ7 Ｃ3 とＮｉ−Ｃｒ合
金相が検出された。この溶射膜の炭素量は、溶射材の状
態で１０・０重量％であったものが溶射膜では６．８重
量％であり、溶射時の脱炭量は３．２重量％であった。
また、熱処理による脱炭量はほとんどなかった。Cr 3 C 2 powder 7 having a particle size of 10 microns
5% by weight and 2 micron diameter Ni-Cr alloy (Ni / C
(r weight ratio = 80/20) 25% by weight of mixed powder was formed into a sprayed film with a thickness of 2 mm under the conditions that a spray current value of 800 amperes was used in an atmospheric plasma spraying apparatus and Ar was used as an arc gas. 1 hour at ℃, Ar,
The heat treatment was performed under the condition of gas atmosphere. The sprayed film when the phase identification Cr 7 C 3 and Ni-Cr alloy phase is detected by X-ray diffraction. The carbon content of this sprayed coating was 10.0 wt% in the sprayed material state, but was 6.8 wt% in the sprayed coating, and the decarburization amount during spraying was 3.2 wt%.
Moreover, the amount of decarburization due to the heat treatment was scarce.
【００４５】この結果に基づいて、上記組成を有するＣ
ｒ3 Ｃ2 とＮｉ−Ｃｒ合金粉末に、粒子径が８ミクロン
の黒鉛を加え、ボールミルで１時間の条件で混合し、上
記の条件で溶射、熱処理を行った。混合物の組成は、Ｃ
ｒ3 Ｃ2 ６８．３重量％、Ｎｉ−Ｃｒ２２．８重量％、
黒鉛８．９重量％であって、Ｃｒ3 Ｃ2 とＮｉ−Ｃｒ合
金の所定組成の重量比が７５：２５の上記溶射材９１．
ｌ重量％に対して、炭素量が８．９重量％多いものであ
った。Based on this result, C having the above composition
Graphite having a particle size of 8 microns was added to r 3 C 2 and Ni—Cr alloy powder, mixed for 1 hour in a ball mill, and sprayed and heat-treated under the above conditions. The composition of the mixture is C
r 3 C 2 68.3 wt%, Ni-Cr22.8 wt%,
The above-mentioned thermal spray material 91.90, which is 8.9% by weight of graphite and has a weight ratio of the predetermined composition of Cr 3 C 2 and Ni—Cr alloy of 75:25.
The carbon content was 8.9% by weight higher than 1% by weight.
【００４６】この溶射材を、上記の黒鉛を余分に加えな
い溶射材と同様の条件で軟鋼に溶射したところ、溶射膜
の炭素量が１０．４重量％となり、さらに上記と同じ条
件で熱処理したところ、Ｃｒ3 Ｃ2 相とＮｉ−Ｃｒ合金
相の２相からなる優良な溶射膜を得ることができた。When this thermal spray material was sprayed on mild steel under the same conditions as the above-mentioned spray material without the addition of graphite, the carbon content of the spray coating became 10.4% by weight, and was further heat-treated under the same conditions as above. However, it was possible to obtain an excellent thermal spray coating consisting of two phases, a Cr 3 C 2 phase and a Ni—Cr alloy phase.
【００４７】以上の実施例の他に、炭化物と金属の組成
比を変えて、層状に形成した溶射膜についても同様の効
果が見られた。In addition to the above examples, the same effect was observed for the thermal spray coating formed in layers by changing the composition ratio of carbide and metal.
【００４８】[0048]
【発明の効果】本発明によって以下の効果を奏する。The present invention has the following effects.
【００４９】（ｌ） 炭素量を調整することで、溶射中
の炭化物の脱炭、溶射後の熱処理にともなう複炭化物の
形成が抑制され、溶射膜の強度と靱性が向上する。(L) By adjusting the amount of carbon, decarburization of carbide during thermal spraying and formation of double carbide due to heat treatment after thermal spraying are suppressed, and the strength and toughness of the thermal spray coating are improved.
【００５０】（２） 炭素量を調整することで、溶射膜
の熱間等方加圧処理の際に生じる複炭化物の形成が抑制
され、低い温度で溶射膜を緻密化することができる。(2) By adjusting the amount of carbon, formation of double carbide that occurs during hot isostatic pressing of the sprayed film can be suppressed, and the sprayed film can be densified at a low temperature.
【００５１】（３） 炭素量を調整することで、熱処理
にともなう複炭化物の形成が抑制され、硬質粒子と結合
金属の組成を徐々に変えることで、熱膨張率の差による
残留応力の緩和をはかることができる。(3) By adjusting the amount of carbon, the formation of double carbide due to the heat treatment is suppressed, and the composition of the hard particles and the binding metal is gradually changed to alleviate the residual stress due to the difference in the coefficient of thermal expansion. You can measure.
【００５２】（４）炭素量を調整することで、熱処理に
伴う熱膨張率の小さい炭化物又は金属の形成が抑制さ
れ、熱膨張差による残留応力の発生を小さくすることが
できる。(4) By adjusting the amount of carbon, formation of carbide or metal having a small coefficient of thermal expansion due to heat treatment can be suppressed, and the occurrence of residual stress due to the difference in thermal expansion can be reduced.
【図１】 本発明の目的を説明するためのＷ−Ｃｏ−Ｃ
系の状態図である。FIG. 1 W-Co-C for illustrating the purpose of the present invention
It is a state diagram of a system.
Claims (3)
らなる溶射材の溶射に際して、溶射材中に、炭化物の脱
炭量に見合う分だけ炭素分を添加配合する炭化物系溶射
膜の形成方法。1. A thermal spray coating of a carbide type, wherein carbon is added to the thermal spray material in an amount commensurate with the decarburization amount of the carbide during thermal spraying of the thermal spray material composed of carbides of group IV, V and VI metals and a bond metal. Forming method.
らなる溶射膜に、該溶射膜を形成する炭化物の脱炭量に
見合う分だけ炭素分を添加配合する炭化物系溶射膜の形
成方法。2. A carbide sprayed film in which a carbon content is added to and mixed with a sprayed film consisting of carbides of group IV, V and VI metals and a bonding metal, in an amount corresponding to the decarburization amount of the carbide forming the sprayed film. Method.
らなる溶射材を溶射し、さらにこの溶射膜に熱処理を加
える場合において、溶射材の溶射に際して溶射材中に、
あるいは溶射膜の熱処理に際して溶射膜中に、炭化物の
脱炭量に見合う分だけ炭素分を添加配合する炭化物系溶
射膜の形成方法。3. When thermal spraying a thermal spray material composed of carbides of group IV, V, and VI metals and a bond metal, and further applying heat treatment to this thermal spray coating, during thermal spraying of the thermal spray material, the thermal spray material contains:
Alternatively, a method for forming a carbide-based sprayed coating in which a carbon content is added and blended in the sprayed coating in an amount corresponding to the decarburization amount of carbide during heat treatment of the sprayed coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4226203A JP2992166B2 (en) | 1992-08-25 | 1992-08-25 | Method of forming sprayed carbide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4226203A JP2992166B2 (en) | 1992-08-25 | 1992-08-25 | Method of forming sprayed carbide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0665710A true JPH0665710A (en) | 1994-03-08 |
| JP2992166B2 JP2992166B2 (en) | 1999-12-20 |
Family
ID=16841512
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4226203A Expired - Lifetime JP2992166B2 (en) | 1992-08-25 | 1992-08-25 | Method of forming sprayed carbide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2992166B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006504234A (en) * | 2002-10-23 | 2006-02-02 | イドロ−ケベック | Particles containing nuclei based on graphite and coated with at least one continuous or discontinuous layer, their preparation and use |
| JP2016079483A (en) * | 2014-10-20 | 2016-05-16 | 株式会社中山アモルファス | Coating for sliding, sliding component, and production method of them |
| JP2020170804A (en) * | 2019-04-04 | 2020-10-15 | 日本タングステン株式会社 | Member for plasma processing device and plasma processing device including the same |
-
1992
- 1992-08-25 JP JP4226203A patent/JP2992166B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006504234A (en) * | 2002-10-23 | 2006-02-02 | イドロ−ケベック | Particles containing nuclei based on graphite and coated with at least one continuous or discontinuous layer, their preparation and use |
| JP4824930B2 (en) * | 2002-10-23 | 2011-11-30 | イドロ−ケベック | Particles containing nuclei based on graphite and coated with at least one continuous or discontinuous layer, their preparation and use |
| JP2016079483A (en) * | 2014-10-20 | 2016-05-16 | 株式会社中山アモルファス | Coating for sliding, sliding component, and production method of them |
| JP2020170804A (en) * | 2019-04-04 | 2020-10-15 | 日本タングステン株式会社 | Member for plasma processing device and plasma processing device including the same |
| US11548827B2 (en) | 2019-04-04 | 2023-01-10 | Nippon Tungsten Co., Ltd. | Member for plasma processing apparatus and plasma processing apparatus with the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2992166B2 (en) | 1999-12-20 |
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