KR100370564B1 - Explosion spray coating method of mixed spray alloy powder - Google Patents
Explosion spray coating method of mixed spray alloy powder Download PDFInfo
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- KR100370564B1 KR100370564B1 KR10-1998-0054791A KR19980054791A KR100370564B1 KR 100370564 B1 KR100370564 B1 KR 100370564B1 KR 19980054791 A KR19980054791 A KR 19980054791A KR 100370564 B1 KR100370564 B1 KR 100370564B1
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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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/126—Detonation spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B7/00—Spraying apparatus for discharge of liquids or other fluent materials from two or more sources, e.g. of liquid and air, of powder and gas
- B05B7/0006—Spraying by means of explosions
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
Abstract
본 발명은 고융점 용사합금과 저융점 용사합금의 혼합분말을 사용하여 폭발용사 코팅을 실시하는 방법에 있어서, 연료가스를 희석가스를 희석시키기 위한 질소가스를 관통(5)에 초기에 주입하여 상기 관통(5)의 선단부에 주입된 질소에 의하여 희석된 희석연료 가스부(30)를 형성한 다음, 산소와 아세틸렌가스를 공급하여 상기 관통(5)의 후부에 희석되지 않은 연료 가스부(29)를 형성하여, 상기 관통(5)에 공급된 고융점 용사합금과 저융점 용사합금의 혼합분말을 선택적으로 폭발용사하여 코팅하는 것을 특징으로 하는 혼합 용사합금분말의 폭발용사 코팅방법을 제공한다.The present invention is a method of performing a thermal spray coating using a mixed powder of a high melting point spray alloy and a low melting point spray alloy, the fuel gas is initially injected through the nitrogen gas for diluting the dilution gas through the (5) After the dilution fuel gas portion 30 is formed by diluting the nitrogen injected into the tip portion of the penetrating portion 5, oxygen and acetylene gas are supplied to the fuel gas portion 29 which is not diluted at the rear portion of the penetrating portion 5. Forming, to provide an explosion spray coating method of the mixed sprayed alloy powder, characterized in that the coating by spraying selectively sprayed powder mixture of the high melting point spray alloy and the low melting point spray alloy supplied to the through (5).
이와 같이, 본 발명에 의하면 고융점 용사합금과 저융점 용사합금을 혼합한 혼합분말로 양호하게 폭발용사코팅을 실시할 수 있음을 알 수 있으며, 코팅층의 박리나 배럴 내부의 고착이 없고 밀착력도 양호한 코팅을 실시할 수 있다.As described above, according to the present invention, it can be seen that the explosive spray coating can be performed with a mixed powder of a high melting point spray alloy and a low melting point spray alloy, and there is no adhesion of the coating layer or adhesion inside the barrel, and the adhesion is also good. Coating can be carried out.
Description
본 발명은 혼합 용사합금분말의 폭발용사 코팅방법에 관한 것으로서, 보다 상세하게는 아세틸렌가스와 산소의 혼합 연료가스에 질소를 일부 혼합하여 고융점 용사합금과 저융점 용사합금으로 이루어진 혼합 용사합금분말의 폭발용사 코팅방법에 관한 것이다.The present invention relates to an explosion spray coating method of a mixed sprayed alloy powder, and more particularly, to a mixed sprayed alloy powder composed of a high melting point spray alloy and a low melting point spray alloy by partially mixing nitrogen with a mixed fuel gas of acetylene gas and oxygen. It relates to an explosion spray coating method.
폭발용사 기술은 1940년대 후반에 아세틸렌 제어 연구로서 기본 구성을 확립한 후에 1953년에 유니온 카바이드(Union Carbide)사에 의해 강력한 폭발에 의해 금속 표면에 경질 피막을 형성시키는 폭발용사장치(Detonation Gun 혹은 D-Gun)가 실용화되었다.Explosion spraying technology is a detonation gun (Dtonation Gun or D) that forms a hard film on a metal surface by a strong explosion by Union Carbide in 1953 after establishing the basic composition as an acetylene control study in the late 1940s. Gun) has been put to practical use.
현재 첨단산업이 발전함에 따라 가혹한 조건인 마모, 부식 분위기 등에서 사용되는 설비, 기계부품, 공구류의 성능 및 수명 향상이 요구되며, 그 방법으로 보호코팅이 사용되고 있고, 폭발용사법은 이러한 보호 코팅을 실시하기 위한 유력한 기술로, 그 사용분야는 항공기, 원자력, 전자부품, 석유화학 등의 산업에 광범위하게 사용되고 있다.As the high-tech industry develops, it is required to improve the performance and lifespan of equipment, machine parts, and tools used in harsh conditions such as abrasion and corrosive atmospheres. As a viable technology, the field of use is widely used in industries such as aircraft, nuclear power, electronic components, and petrochemicals.
일반적으로 폭발 용사는 카바이드 세라믹 및 금속합금 등의 다양한 물질을 코팅할 수 있는데, 일정한 폭발 반응식으로는 적절한 폭발 온도를 형성시키지 못하므로 질소량을 조절하여 폭발용사 코팅 조건을 맞추고 있다.In general, the thermal spraying can coat a variety of materials, such as carbide ceramics and metal alloys, and because the constant explosion reaction does not form a proper explosion temperature, by adjusting the amount of nitrogen to meet the spraying coating conditions.
그러나, 융점의 차이가 큰 혼합합금을 폭발용사코팅할 경우에는 용사조건을 설정하는데 있어서 문제가 발생한다.However, when the thermal spray coating of a mixed alloy having a large difference in melting point occurs, there is a problem in setting the thermal spraying conditions.
예를 들어 폭발온도를 고온의 용사합금에 설정할 경우 저융점 용사합금은 과도한 용융에 의해 코팅층의 잔류응력을 증가시켜 코팅층이 박리되고 심한 경우 배럴 내부에 고착되어 코팅에 문제가 발생하기 쉽다.For example, when the explosion temperature is set to a high temperature sprayed alloy, the low melting sprayed alloy increases the residual stress of the coating layer due to excessive melting, so that the coating layer is peeled off.
또한, 저융점 용사합금에 적절한 용사조건을 설정하면 고융점 용사합금은 용융되지 아니하여 밀착력에 악영향을 초래한다.In addition, if proper spraying conditions are set for the low-melting-point sprayed alloy, the high-melting-point sprayed alloy is not melted and thus adversely affects the adhesion.
상기한 문제점을 해결하기 위하여, 본 발명은 고융점 및 저융점의 용사합금을 동시에 코팅하기 위한 수단으로 질소를 공급하여 연료가스와 희석시킨 희석연료 가스부를 형성시켜 선택적으로 폭발 온도를 낮춤으로써 고융점 및 저융점의 용사합금의 혼합합금을 동시에 용사코팅할 수 있는 혼합 용사합금분말의 폭발용사 코팅방법을 제공함에 그 목적이 있다.In order to solve the above problems, the present invention forms a dilution fuel gas portion diluted with fuel gas by supplying nitrogen as a means for simultaneously coating a high melting point and a low melting point spray alloy, thereby selectively lowering the explosion temperature. And it is an object of the present invention to provide a spray coating method of the sprayed mixed alloy powder powder can be sprayed on the mixed alloy of the sprayed alloy of low melting point at the same time.
도 1 은 폭발용사코팅을 실시하기 위한 장치를 개략적으로 도시한 도면,1 schematically shows an apparatus for carrying out a thermal spray coating,
도 2 는 관통에 가스를 공급하는 계통을 도시한 도면,2 is a diagram showing a system for supplying gas to the penetration;
도 3 은 폭발용사코팅장치에서의 종래의 밸브 시퀀스를 도시한 도면,3 is a view showing a conventional valve sequence in the thermal spray coating apparatus,
도 4 는 본 발명에 따른 혼합 용사합금분말의 폭발용사 코팅방법을 실시하기위한 밸브 시퀀스를 도시한 도면,4 is a view showing a valve sequence for carrying out a method for spray coating of the sprayed mixed alloy powder in accordance with the present invention,
도 5 는 본 발명에 따른 혼합 용사합금분말의 폭발용사 코팅방법을 실시하기 위해 관통에 희석연료 가스부를 형성한 구성을 도시한 도면,5 is a view showing a configuration in which a dilution fuel gas portion is formed in the penetration to perform the explosion spray coating method of the mixed spray alloy powder according to the present invention;
도 6 은 본 발명에 따른 혼합 용사합금분말의 폭발용사 코팅방법을 실시하여 획득된 코팅층의 조직사진이다.Figure 6 is a tissue photograph of the coating layer obtained by performing a sprayed spray coating method of the mixed sprayed alloy powder according to the present invention.
〈도면의 주요부분에 대한 부호의 설명〉<Explanation of symbols for main parts of drawing>
5: 관통(Barrel) 7: 가스공급장치 8: 제어장치5: Barrel 7: Gas Supply Unit 8: Control Unit
11: 파우더공급장치 13: 모재 14: 코팅층11: powder supply device 13: base material 14: coating layer
29: 연료 가스부 30: 희석연료가스부29: fuel gas unit 30: dilution fuel gas unit
상기 목적을 달성하기 위하여, 본 발명의 고융점 용사합금과 저융점 용사합금의 혼합분말을 사용하여 폭발용사 코팅을 실시하는 방법에 있어서, 연료가스를 희석시키기 위한 질소가스를 관통에 초기에 주입하여 상기 관통의 선단부에 주입된 질소에 의하여 희석된 희석연료 가스부를 형성한 다음, 산소와 아세틸렌가스를 공급하여 상기 관통의 후부에 희석되지 않은 연료 가스부를 형성하여, 상기 관통에 공급된 고융점 용사합금과 저융점 용사합금의 혼합분말을 선택적으로 폭발용사하여 코팅하는 것을 특징으로 하는 혼합 용사합금분말의 폭발용사 코팅방법을 제공한다.In order to achieve the above object, in the explosion spray coating method using the powder mixture of the high-melting-point spray alloy and the low-melting point spray alloy of the present invention, nitrogen gas for diluting fuel gas is initially injected through After forming a diluted fuel gas portion diluted by nitrogen injected into the tip of the through, supplying oxygen and acetylene gas to form a fuel gas portion undiluted at the rear of the through, the high melting point spray alloy supplied to the through The present invention provides an explosion spray coating method of a mixed sprayed alloy powder, characterized in that the spray coating and spraying the powder of the low melting point spray alloy selectively.
이하에서는 양호한 실시예를 도시한 첨부도면과 관련하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings showing preferred embodiments.
도 1 은 아세틸렌가스를 이용하여 폭발용사코팅을 실시하는 장치의 계통을도시하고 있는데, 1∼1.5m 길이 및 20∼30㎜ 직경을 가지는 관통(5)과, 이 관통에 용사합금 분말을 공급하는 파우더 공급장치(11), 관통에 공급된 분말을 점화시키는 점화장치(4), 및 각종 가스공급원(1,2,3)으로부터 관통에 가스를 공급하기 위한 가스공급장치(7)와, 분말공급장치(11) 및 가스공급장치(7) 및 분말공급장치(11)의 밸브를 작동시키기 위한 밸브기어(6) 및 밸브 드라이브(10)와, 이들을 제어하기 위한 제어장치(8)를 구비하고, 이 제어장치(8)에는 또한 코팅층(14)을 형성할 모재(13)가 장착된 매니플레이터(Minipulator; 12)가 전기적으로 연결되며, 제어 작동을 디스플레이하기 위한 컴퓨터(9)가 연결된다.FIG. 1 shows a system of an apparatus for performing thermal spray coating using acetylene gas, which has a penetration 5 having a length of 1 to 1.5 m and a diameter of 20 to 30 mm, and supplying the spray alloy powder to the penetration. A powder supply device 11, an ignition device 4 for igniting the powder supplied to the penetration, and a gas supply device 7 for supplying gas to the penetration from various gas supply sources 1, 2 and 3, and powder supply. A valve gear 6 and a valve drive 10 for operating the valves of the device 11 and the gas supply device 7 and the powder supply device 11, and a control device 8 for controlling them; The control device 8 is also electrically connected to a manipulator 12 equipped with a base material 13 on which the coating layer 14 is to be formed, and to a computer 9 for displaying control operation.
도 2의 도시와 같이, 상기 장치를 통한 각종 가스가 공급되어 관통에서 폭발하여 용사 코팅을 실시하는 경로를 보면, 산소가스공급원(1) 및 아세틸렌가스공급원(3)으로부터 라인(19,20)을 통해 밸브(23,24)를 거쳐 산소 및 아세틸렌가스는 혼합실(18)로 공급되어 순식간에 혼합된 후, 혼합실밸브(25)를 통해 완충실(17)로 들어가고 관통밸브(26)를 거쳐 점화플러그(16)가 설치된 관통(5)으로 유동하여 파우더 공급장치(11)를 통해 용사합금 분말이 공급되면 점화되어 폭발 용사코팅을 실시하여 용사코팅 작업을 수행하는데, 이러한 작동을 제어하는 밸브 개폐 시퀀스가 도 3 및 도 4 에 도시되고 있다.As shown in FIG. 2, a route through which various gases are supplied through the apparatus and exploded in penetration to apply a spray coating is shown. Lines 19 and 20 are separated from the oxygen gas supply source 1 and the acetylene gas supply source 3. Oxygen and acetylene gas are supplied to the mixing chamber 18 through the valves (23, 24) through the mixing chamber 18, and then enters the buffer chamber 17 through the mixing chamber valve 25 and through the through valve 26 When the spray alloy powder is supplied through the powder supply device 11 by flowing through the penetrating 5 having the spark plug 16 installed thereon, it is ignited to perform a thermal spray coating by performing a thermal spray coating. The sequence is shown in FIGS. 3 and 4.
이와같은 과정을 통해 실시되는 폭발용사 코팅의 원리를 설명하면 다음과 같다.When explaining the principle of the spray coating carried out through the process as follows.
폭발에 필요한 연료로 작용하는 아세틸렌과 산소가 혼합하여 점화되어 초당 2∼8회 단속적으로 폭발을 일으키는데, 이때 질소는 각종 라인을 청소시키고 화염온도를 낮추는 역할을 한다.Acetylene and oxygen, which act as fuels required for the explosion, are ignited and ignited, causing an explosion two to eight times per second. At this time, nitrogen cleans various lines and lowers the flame temperature.
폭발용사시 관통(5) 내의 폭발 반응식은 다음과 같다.The explosion reaction formula in the penetration (5) during the explosion spray is as follows.
C2H2+ O2+ 2N2→2CO + H2+ N2 C 2 H 2 + O 2 + 2 N 2 → 2CO + H 2 + N 2
도 3 및 도 4 의 밸브 시퀀스를 통해 산소와 아세틸렌 및 프로판 가스의 몰비에 따른 폭발온도와 속도를 알 수 있는데, 이러한 온도와 속도는 용사코팅에서 가장 중요한 요소이며, 산소와 아세틸렌의 적정 몰비는 이론적으로 1:1이지만 폭발이 안정적으로 일어나도록 하기 위하여 산소량을 조금 높게 해준다.3 and 4 shows the explosion temperature and speed according to the molar ratio of oxygen, acetylene and propane gas. The temperature and speed are the most important factors in the thermal spray coating, and the proper molar ratio of oxygen and acetylene is theoretical. 1: 1, but raises the oxygen content a little so that the explosion can occur stably.
여기서, 질소는 연료를 희석시켜 폭발 온도를 낮추도록 작용하며, 주로 저융점의 용사합금을 사용하여 코팅시 사용한다.Here, nitrogen acts to lower the explosion temperature by diluting the fuel, and is mainly used for coating using a spray alloy of low melting point.
본 발명에서는 이러한 질소 가스의 특성을 선택적으로 사용할 수 있음에 착안하였다.In the present invention, it was conceived that these characteristics of nitrogen gas can be selectively used.
종래에는 도 3 도시와 같이, 아세틸렌과 산소 밸브가 개방된 시간에는 질소가 관통(5)으로 주입될 수 없었다.Conventionally, as shown in FIG. 3, nitrogen could not be injected into the penetrating 5 at the time when the acetylene and oxygen valves were opened.
본 발명에서는 도 5 도시와 같이, 일정량의 질소 가스를 관통(5) 내부에 스카밴징 밸브(Scavenging Valve; 31-1)를 이용하여 초기에 주입하고, 이어서 산소와 아세틸렌가스를 공급함으로써, 관통(5)의 선단부에는 질소에 의해 희석된 희석연료연료 가스부(30)를 형성하고, 그 후부에 희석되지 않은 연료 가스부(29)를 형성하여 혼합합금 분말을 관통(5)에 공급시 선택적으로 폭발이 발생하도록 구성하여 용사코팅을 실시한다.In the present invention, as shown in FIG. 5, a certain amount of nitrogen gas is initially injected into the penetrating 5 using a scavenging valve 31-1, and then oxygen and acetylene gas are supplied to thereby penetrate ( The dilution fuel gas part 30 diluted with nitrogen is formed in the front-end | tip part of 5), and the fuel gas part 29 which is not diluted is formed in the back part, and the mixed alloy powder is selectively supplied at the time of supplying the mixed alloy powder to the penetrating (5). Explosion-prone coatings are configured to generate an explosion.
여기서, 질소를 관통(5)에 공급시 종래의 일반적인 질소밸브(31)를 이용하지 않고, 스카벤징 밸브(31-1)를 이용하는 것은 그 직경이 더 크기 때문에 짧은 시간에 효과적으로 연료와 질소를 혼합하여 폭발온도를 낮추기 위한 것이며, 상기 스카밴징 밸브(Scavenging Valve; 31-1)는 일반적으로 소기(掃氣) 공기가 모여 있는 곳에 설치되는 소기공기 흡입용 밸브를 일컫는 것이다.Here, the use of the scavenging valve 31-1 without the conventional general nitrogen valve 31 when supplying nitrogen to the penetrating (5), because the diameter is larger, it effectively mixes fuel and nitrogen in a short time By lowering the explosion temperature, the scavenging valve (Scavenging Valve; 31-1) is generally referred to as a small air intake valve is installed where the scavenged air (모여) is collected.
이와같이, 질소에 의해 희석된 희석연료 가스부(30)가 혼합합금 중에서 저융점 용사합금만 선택적으로 반용융시키고, 고융점 합금은 희석되지 않은 연료가스부 (29)에 의해 고온의 폭발력에 의해 선택적으로 코팅이 이루어지게 되는 것이다.As such, the dilution fuel gas portion 30 diluted with nitrogen selectively semi-melts only the low-melting-point spray alloy in the mixed alloy, and the high-melting-point alloy is selectively selected by the high-temperature explosive force by the undiluted fuel gas portion 29. The coating is to be made.
이하에서는 실시예와 관련하여 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
[실시예]EXAMPLE
동판의 모재에 고융점의 텅스텐카바이드(WC-20Co)와 저융점(900∼100℃)의 Ni계 자용성 용사합금을 5:5로 혼합하여 표 1 에 나타낸 바와같은 코팅 조건으로 용사코팅을 실시한 후 코팅층의 조직을 관찰하여 혼합합금을 사용한 용사코팅이 가능한지 시험하였다.The copper base metal was mixed with a high melting tungsten carbide (WC-20Co) and a low melting point (900 to 100 ° C.) Ni-based soluble thermally sprayed alloy at 5: 5, followed by spray coating under the coating conditions shown in Table 1. After observing the structure of the coating layer it was tested whether the spray coating using the mixed alloy is possible.
[표 1]TABLE 1
도 6 은 본 발명이 적용된 저융점 용사합금과 고융점 합금의 혼합합금을 사용하여 폭발용사코팅을 실시 후 얻어진 코팅층의 미세조직사진인데, 백색 부분은WC 의 입자이나, 흑색 부분은 금속합금(Metallic Alloy)으로 저융점 용사합금과 고융점 용사합금이 혼합 용융되어 형성된 조직을 나타내고 있는 바, 선택적으로 폭발용사가 이루어져 양호한 코팅층을 형성하고 있음을 알 수 있다.Figure 6 is a microstructure photograph of the coating layer obtained after performing the thermal spray coating using a mixture of a low melting point spray alloy and a high melting point alloy applied to the present invention, the white portion is WC particles, the black portion is a metal alloy (Metallic Alloy) shows a structure formed by mixing and melting a low melting point spray alloy and a high melting point spray alloy, and it can be seen that an explosion is selectively formed to form a good coating layer.
따라서, 상술한 바와같이, 본 발명에 의하여 질소가스를 연료 희석용 가스로 이용함으로써 고융점 합금과 저융점 용사합금을 혼합한 혼합합금으로 양호하게 용사코팅을 실시할 수 있음을 알 수 있으며, 코팅층의 박리나 배럴 내부의 고착이 없고 밀착력도 양호한 코팅을 실시할 수 있다.Therefore, as described above, it can be seen that by using the nitrogen gas as the fuel dilution gas according to the present invention, it is possible to satisfactorily spray coating with a mixed alloy of a high melting point alloy and a low melting point spray alloy. It is possible to perform coating with good adhesion without peeling or sticking inside the barrel.
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| KR19990055018A (en) * | 1997-12-27 | 1999-07-15 | 신현준 | Explosion spray coating method using propane |
| US6258416B1 (en) * | 1996-06-28 | 2001-07-10 | Metalspray U.S.A., Inc. | Method for forming a coating on a substrate by thermal spraying |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04218657A (en) * | 1990-02-06 | 1992-08-10 | Air Prod And Chem Inc | Promotion method of abrasion resistance of support and product therefrom |
| US6258416B1 (en) * | 1996-06-28 | 2001-07-10 | Metalspray U.S.A., Inc. | Method for forming a coating on a substrate by thermal spraying |
| KR19990055018A (en) * | 1997-12-27 | 1999-07-15 | 신현준 | Explosion spray coating method using propane |
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