EP0381760B1 - Method of forming ceramic layer on metallic body - Google Patents

Method of forming ceramic layer on metallic body Download PDF

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Publication number
EP0381760B1
EP0381760B1 EP89905209A EP89905209A EP0381760B1 EP 0381760 B1 EP0381760 B1 EP 0381760B1 EP 89905209 A EP89905209 A EP 89905209A EP 89905209 A EP89905209 A EP 89905209A EP 0381760 B1 EP0381760 B1 EP 0381760B1
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EP
European Patent Office
Prior art keywords
powder
metallic
ceramic
metallic body
ceramic 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.)
Expired - Lifetime
Application number
EP89905209A
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German (de)
English (en)
French (fr)
Other versions
EP0381760A4 (en
EP0381760A1 (en
Inventor
Shyuichi Takeda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Komatsu Ltd
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Komatsu Ltd
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Filing date
Publication date
Application filed by Komatsu Ltd filed Critical Komatsu Ltd
Publication of EP0381760A1 publication Critical patent/EP0381760A1/en
Publication of EP0381760A4 publication Critical patent/EP0381760A4/en
Application granted granted Critical
Publication of EP0381760B1 publication Critical patent/EP0381760B1/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/08—Compacting only by explosive forces

Definitions

  • This invention relates to a method of forming a compact ceramic layer on a metallic body, and more particularly to a method of forming a compact ceramic layer having an enhanced adhesion to the metallic body by utilizing a great deal of heat developed momentarily by Thermit reaction which occurs conveniently under a pressurized condition.
  • JP-A-62-238 303 discloses a method in which the heat of Thermit reaction is used for bonding a composite metallic body such as WC-Co to a metallic body, e.g. copper. However, this document does not disclose a method for bonding a ceramic layer to a metallic body.
  • US-A-4 363 832 discloses a method for forming a ceramic lining layer on the inward surface of a hollow body such as a pipe.
  • a Thermit mixture is disposed inside of the hollow body, and the hollow body is rotated at a high speed so that the Thermit mixture is pressed against the wall of the hollow body.
  • the Thermit composition is ignited, so that the molten metal generated in the Thermit reaction flows outwardly due to the centrifugal forces, and a ceramic lining at the internal surface of the metal body is formed by the oxide of the strongly reductive component of the Thermit composition.
  • the ceramic layer can only be formed by materials which are part of the initial Thermit composition.
  • the method of forming a ceramic layer on a metallic body according to the present invention is a process which utilizes the sudden generation of heat by Thermit reaction and the exothermic reaction of a ceramic compound which is induced effectively and efficiently by the Thermit reaction, various kinds of non-oxidizing ceramics, which were difficult to sinter and which could provide a compact ceramic layer only by using a binder, can be used to form a compact ceramic layer without having to use a binder, and also they can provide an enhanced adhesion to a metallic body.
  • the method of the present invention provides another advantage in that since the heating time is very short the ceramic crystal growth can be restrained markedly thus reducing thermal damage of the metallic body. Further, in addition to the characteristic feature of the method of forming a ceramic layer using Thermit reaction, the resistance to corrosion, resistance to heat and resistance to abrasion of the ceramic layer can be improved markedly by limiting the content of oxygen which is an impurity existent unavoidably in powdery raw materials to a particular range and by limiting the particle diameter of the powdery raw material in the same way so that various kinds of very excellent ceramic layers can be provided.
  • the method of the present invention can be widely used to form excellent lens forming molds, provision of which has come to be required with the recent improvement in the performance of glass lenses, various kinds of materials for chemical industry for use in severe environmental conditions, and various kinds of mechanical parts which require high resistance to abrasion, and can therefore contribute to industrial development.
  • Fig. 1 is a sectional view showing one embodiment of the pressing apparatus adapted for use in the method of the present invention.
  • Fig. 1 shows a manufacturing apparatus which is used to form a ceramic layer on a metallic body according to the present invention.
  • reference numeral 1 denotes a cylinder, 2 a pressing punch, 3 a platform made of a metal or ceramic, 4 a cylinder made of a ceramic, 4a a plate, 5 an electric wire made of a ceramic, 6 a Si-Thermit composition, 7 an Al-Thermit composition, 8 a hexagonal boron nitride molded article, 9 a ceramic powder or a mixture of a metallic powder with a ceramic powder for providing a compact ceramic layer, and 10 a metallic body for forming a ceramic layer thereon.
  • the cylinder 1, the pressing punch 2 and the metal platform 3 form a pressure generating vessel, whilst the ceramic cylinder 4 serves as a thermal insulation material and a pressure seal.
  • the electric wire 5 made of a ceramic constitutes an internal heater to ignite the Si-Thermit composition 6 to thereby ignite the Al-Thermit composition 7 with a chain-reaction.
  • the hexagonal system boron nitride molded article 8 functions to prevent reaction from occurring between the ceramic layer 9 to be formed on the metallic body and the Thermit compositions 6 and 7 and serves to achieve excellent condition of the heat generated by Thermit reaction.
  • the metallic body 10 on which a ceramic powder or a mixture 9 of a ceramic powder with a metallic powder is placed is disposed on the metal platform 3 forming the bottom wall of the cylinder 1. Further, the hexagonal system boron nitride molded article 8 is placed on the ceramic powder or the mixture, and then the Al-Thermit composition 7 around which the Si-Thermit composition 6 is placed is disposed on the molded article 8. Further, the ceramic plate 4a is placed on the Si-Thermit composition. Thereafter, a load is applied by means of the pressing punch 2 so as to apply more than 50 MPa (500 atmospheres) of pressure onto the ceramic powder or mixture 9 of a ceramic powder with a metal powder.
  • MPa 500 atmospheres
  • the Si-Thermit composition 6 disposed around the Al-Thermit composition 7 is ignited thereby causing the ignition of the Al-Thermit composition with a chain-reaction thus generating a great deal of heat by the Thermit reaction.
  • the time series chemical reaction commencement of the Thermit compositions is represented by the following formula. Si + 2/3Fe2O3 ⁇ SiO2 + 4/3Fe + 360 KJ (86 Kcal) 2Al + Fe2O3 ⁇ Al2O3 + 2Fe + 854 KJ (204 Kcal)
  • a fine ceramic layer is formed on the metallic body by the heat developed by the ignition of the Thermit composition. After that, the loading is released, and the sample is recovered.
  • TiB2 powder having an oxygen content of 0.6 % and a mean particle diameter of 1.0 »m to be used as the ceramic powder 9 was placed on a 4.0% Co-WC disc having a diameter of 6.0 mm and a thickness of 2.5 mm.
  • Thermit composition 42 gr of a Thermit composition prepared by mixing Al powder and Fe2O3 powder at a molar ratio of 2 : 1 was cold molded on a disc having a diameter of 30 mm.
  • 6 gr of a Si-Thermit composition was placed in the above-mentioned manufacturing apparatus to form a compact ceramic layer.
  • the amount of heat generated by Thermit reaction in this example was 183 KJ (43.8 Kcal.)
  • the ground surface had silver luster.
  • the hard metal pellet obtained in this example was cut by means of a diamond cutter, and then ground. As a result of observation of the cut portion by SEM, it revealed that the adhesive interface between the ceramic layer and the WC-4% Co disc exhibited an extremely excellent adhesion.
  • a ceramic layer (stating exactly, cermet layer) was formed under the same conditions as in EXAMPLE 1, except that 0.1 gr of a mixture of TiB2 and Ni (percent of Ni by volume: 3%) was used as the ceramic powder and metal powder 9 used in EXAMPLE 1, the oxygen contents of TiB2 and Ni were set at 0.6% and 0.4%, respectivley, and the mean particle diameters of TiB2 and Ni were set at 1.0 »m and 3.0 »m, the heat value by Thermit reaction was set at 146 KJ (35 KCAL) and carbon steel was used as the material of the metallic body 10.
  • a ceramic layer was formed under the same conditions as in EXAMPLE 1, except that 0.02 - 0.04 gr of each of TiC (oxygen content: 0.5%, mean particle diameter: 1.2 »m), TiN (oxygen content: 0.7%, mean particle diameter: 1.0 »m) , and TiC 0.5 N 0.5 (oxygen content: 0.8%, mean particle diameter: 1.3 »m) were used as the ceramic powder 9 in EXAMPLE 1, the heat value by Thermit reaction was set at 167 KJ (40 KCAL), and stainless steel was used as the material of the metallic body.
  • the ceramic layer obtained in this example exhibited extremely excellent performance as in the case of EXAMPLE 1.
  • a ceramic layer was formed under the same conditions as in EXAMPLE 1, except that, as the ceramic powder 9, 0.01 gr of B4C (oxygen content: 0.8%, mean particle diameter: 2 »m) was placed on a 4% Co-WC disc, and further 0.2 gr of a mixture of Ti powder and B powder in a molar ratio of 1 : 2 was placed in layer, and the heat value by Thermit reaction was set at 146 KJ (35 KCAL).
  • the ceramic layer resulted from the mixture of TiB2, B4C and TiC in this example provided an extremely compact hard layer having an excellent adhesion to the metallic body 10.
  • a ceramic layer was formed under the same conditions as in EXAMPLE 1, except that 0.03 gr of a mixture of Ti powder (mean particle diameter: 5 »m, oxygen content: 0.5%) and B powder (mean particle diameter: 0.5 »m, oxygen content: 0.8%) in a molar ratio of 1 : 2, and 0.02 gr of a mixture of Si powder (mean particle diameter: 2 »m, oxygen content: 0.6%) and C powder (mean particle diameter: 3 »m, oxygen content: 0.5%) in a molar of 1 : 1 were placed on a stainless steel disc, in place of the ceramic powder 9, and the heat value by Thermit reaction was set at 126 KJ (30 KCAL).
  • a ceramic layer was formed under the same conditions as in the case of EXAMPLE 1, except that, in place of the ceramic powder 9, 0.06 gr of a mixture of B4C powder (whose oxygen content and mean particle diameter were the same as those in EXAMPLE 4) and Ti powder (whose oxygen content and mean particle diameter were the same as those in EXAMPLE 5) in a molar ratio of 4 : 1 was placed on a 4% Co-WC hard metal disc, and the heat value by Thermit reaction was set at 146 KJ (35 KCAL).
  • the resultant ceramic layer was comprised of B4C, TiB2 and TiC and exhibited a satisfactory compactness and an excellent adhesion to the metallic body.
  • a ceramic layer was formed under the same conditions as in the case of EXAMPLE 1, except that a thin Ta plate, 0.05 mm thick, was previously placed on the metallic body 10, 0.02 gr of ZrN powder (mean particle diameter: 1 »m, oxygen content: 1%) was placed, as the ceramic powder, on the thin plate, and the heat value by Thermit reaction was set at 146 KJ (35 KCAL).
  • the Ta thin plate used in this example was effective for relaxing the thermal stress on the ceramic layer and the metallic body and forming an extremely excellent crack-free ceramic layer.
  • a ceramic layer was formed under the same conditions as in the case of EXAMPLE 1, except that a mixture of TiB2 and Ni4B3 (in a volume ratio of 6 : 4) was used as the ceramic powder 9 in EXAMPLE 1, a Ni-Ti thin plate, 0.05 mm thick, was previously placed on the metallic body, and the heat value by Thermit reaction was set at 126 KJ (30 KAL).
  • the ceramic/WC-Co composite body obtained by this ceramic layer forming method was subjected to HIP (hot hydrostatic pressure pressing) treatment in an Argon atmosphere kept at a temperature of 600°C and a 100 MPa (1,000 atmospheres) of pressure, for 30 minutes.
  • HIP hot hydrostatic pressure pressing
  • a ceramic layer was formed using TiB2 powder having an oxygen content of 1.8%, according to a similar procedure to that in EXAMPLE 1.
  • the resultant ceramic layer was less compact than that in the case of using the powder with a low oxygen content in EXAMPLE 1 and exhibited an inferior adhesion to the 4% Co-WC hard metal disc.
  • the particle diameter of the crystal of TiB2 forming the ceramic layer grew partially abnormally, and in a heating and cooling cycle at a temperature ranging from a room temperature in the atmosphere to 700°C, a portion of the ceramic layer broke down.
  • oxygen which is an unavoidably existent impurity, lowered the compactness of the ceramic layer and the adhesion to the metallic body.
  • a ceramic layer was formed using TiC powder having a mean particle diameter of 15 »m, according to a similar procedure to that in EXAMPLE 3.
  • the compactness of the resultant ceramic layer deteriorated, and in most cases molten metal from the substrate metallic body intruded into the ceramic layer. Similar troubles occurred in EXAMPLE 1 to 6. Further, in particular, in cases of ceramics having strong thermal anisotropy in the crystal structure thereof, a great many intergranular cracks occur with the increase in the crystalline particle diameter thus increasing the frequency of occurrence of break-down.
  • the ceramic compound layer resulted from a starting material such metallic elements/non-metallic elements as shown in EXAMPLE 5 will contain non-reacted metallic elements and non-metallic elements. It is necessary to keep the mean particle diameter of powdery raw materials 10 »m or under.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Powder Metallurgy (AREA)
EP89905209A 1988-04-21 1989-04-21 Method of forming ceramic layer on metallic body Expired - Lifetime EP0381760B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP63098827A JP2717541B2 (ja) 1988-04-21 1988-04-21 金属体上へのセラミック層形成方法
JP98827/88 1988-04-21
PCT/JP1989/000429 WO1989010432A1 (en) 1988-04-21 1989-04-21 Method of forming ceramic layer on metallic body

Publications (3)

Publication Number Publication Date
EP0381760A1 EP0381760A1 (en) 1990-08-16
EP0381760A4 EP0381760A4 (en) 1990-10-10
EP0381760B1 true EP0381760B1 (en) 1995-01-18

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EP89905209A Expired - Lifetime EP0381760B1 (en) 1988-04-21 1989-04-21 Method of forming ceramic layer on metallic body

Country Status (4)

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EP (1) EP0381760B1 (ja)
JP (1) JP2717541B2 (ja)
DE (1) DE68920726T2 (ja)
WO (1) WO1989010432A1 (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112654A (en) * 1990-06-25 1992-05-12 Lanxide Technology Company, Lp Method for forming a surface coating
US5250324A (en) * 1990-06-25 1993-10-05 Lanxide Technology Company, L.P. Method for forming a surface coating using powdered solid oxidants and parent metals
FR2665385B1 (fr) * 1990-08-02 1992-10-16 Sintertech Procede et dispositif de revetement d'une piece comportant une surface inclinee a revetir de poudre en couche mince.
US6510694B2 (en) 2000-07-10 2003-01-28 Lockheed Corp Net molded tantalum carbide rocket nozzle throat
CN104057086B (zh) * 2014-07-10 2016-04-20 哈尔滨工业大学 钛铝金属-六方氮化硼陶瓷导电阴极材料的制备方法
KR101762679B1 (ko) * 2016-10-21 2017-08-14 주식회사 웨어솔루션 세라믹으로 코팅된 강판의 제조방법

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56150190A (en) * 1980-01-16 1981-11-20 Agency Of Ind Science & Technol Preparation of composite material by thermite reaction
JPS5983982A (ja) * 1982-10-30 1984-05-15 工業技術院長 複合構造体の製造法
JPS59179335A (ja) * 1983-03-30 1984-10-11 工業技術院長 複合構造ライニング管の製造方法
JPS6027462A (ja) * 1983-07-26 1985-02-12 Agency Of Ind Science & Technol 複合構造管の製造方法
JPS6179777A (ja) * 1984-09-26 1986-04-23 Agency Of Ind Science & Technol 複合管の製造方法
JPH0791567B2 (ja) * 1985-02-15 1995-10-04 株式会社小松製作所 焼結方法
JPS62156271A (ja) * 1985-12-27 1987-07-11 Agency Of Ind Science & Technol 高融点無機化合物の厚肉コ−テイング方法
JPS62238303A (ja) * 1986-04-10 1987-10-19 Komatsu Ltd 金属体と金属基複合材料の接合体の製造方法
JPS62253703A (ja) * 1986-04-28 1987-11-05 Komatsu Ltd テルミツト加熱方法
JPS6389677A (ja) * 1986-10-01 1988-04-20 Agency Of Ind Science & Technol 厚肉セラミツクコ−テイング方法
JPS6389676A (ja) * 1986-10-01 1988-04-20 Agency Of Ind Science & Technol 厚肉セラミツクコ−テイング方法

Also Published As

Publication number Publication date
JP2717541B2 (ja) 1998-02-18
WO1989010432A1 (en) 1989-11-02
EP0381760A4 (en) 1990-10-10
JPH01272770A (ja) 1989-10-31
DE68920726D1 (de) 1995-03-02
DE68920726T2 (de) 1995-05-18
EP0381760A1 (en) 1990-08-16

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