KR100307504B1 - Metal Surface Treatment by Chroming and Ion Nitriding - Google Patents
Metal Surface Treatment by Chroming and Ion Nitriding Download PDFInfo
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- KR100307504B1 KR100307504B1 KR1019980048049A KR19980048049A KR100307504B1 KR 100307504 B1 KR100307504 B1 KR 100307504B1 KR 1019980048049 A KR1019980048049 A KR 1019980048049A KR 19980048049 A KR19980048049 A KR 19980048049A KR 100307504 B1 KR100307504 B1 KR 100307504B1
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
- C23C10/32—Chromising
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/02—Pretreatment of the material to be coated
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
Abstract
본 발명은 니켈이나 철계 합금의 표면에 내산화성과 내마모성이 우수한 질화크롬(CrN) 상(相)을 형성시키는 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법에 관한 것으로서, 본 발명은 시료의 표면을 크롬으로 처리하는 크로마이징(chromizing)단계와, 상기 크롬처리된 시료의 표면을 질소이온으로 질화처리하는 이온질화처리단계로 이루어진 본 발명의 금속표면처리방법에 의하면, 질화크롬(CrN) 상(相)의 형성 방법이 단순하고 전면에 대해서 처리가 용이한 장점이 있으며, 확산에 의해 모재표면의 조성이 변하면서 코팅층을 형성하기 때문에 처리 온도와 시간에 따라 두꺼운 코팅층을 얻을 수 있을 뿐만 아니라 온도 변화가 심한 환경에서도 층의 박리가 일어나지 않는다. 또한, 제품의 형상에 영향을 거의 받지 않고 표면 처리가 가능하며 질화크롬(CrN) 상(相)을 형성시키는 종래의 방법에 비해 저렴한 가격으로 처리가 가능하다.The present invention relates to a metal surface treatment method by chromizing and ion nitriding to form a chromium nitride (CrN) phase excellent in oxidation resistance and abrasion resistance on the surface of nickel or iron-based alloy, the present invention According to the metal surface treatment method of the present invention comprising a chromizing step of treating the surface of a sample with chromium and an ion nitriding step of nitriding the surface of the chrome treated sample with chromium nitride, CrN ) The method of forming the phase is simple, and it is easy to process on the entire surface. Since the composition of the base material surface is changed by diffusion, the coating layer is formed, so that a thick coating layer can be obtained depending on the processing temperature and time. However, no peeling of the layer occurs even in a severe temperature change environment. In addition, the surface treatment can be performed almost without being affected by the shape of the product, and it can be processed at a lower cost than the conventional method of forming a chromium nitride (CrN) phase.
그리고, 고온에서 안정한 질화크롬(CrN) 상(相)에 의해 우수한 고온 내산화 특성을 얻을 수 있음과 동시에, 우수한 고온 내마모 특성을 얻을 수 있는 효과가 있다.In addition, an excellent high temperature oxidation resistance can be obtained by the chromium nitride (CrN) phase stable at high temperature, and an excellent high temperature wear resistance can be obtained.
Description
본 발명은 니켈이나 철계 합금의 표면에 내산화성과 내마모성이 우수한 질화크롬(CrN) 상(相)을 형성시키는 표면처리방법에 관한 것이다.The present invention relates to a surface treatment method for forming a chromium nitride (CrN) phase having excellent oxidation resistance and wear resistance on a surface of nickel or iron alloy.
종래에는 일반적으로 금속의 표면 위에 물리적 기상 증착법(PVD)을 이용하여 질화크롬(CrN) 상(相,phase)을 증착시키는 방법을 이용하였으며, 이것은 고진공 상태에서 크롬의 증기와 질소원자를 기체상태에서 금속표면에 동시에 반응시켜서 재료의 표면 위에 질화크롬(CrN) 상(相)을 박막의 형태로 형성시키는 것으로서, HCD법, 마그네트론 스퍼터링법, 반응성 이온 플레이팅법, 음극 아크 증발법 등이 있다.Conventionally, chromium nitride (CrN) phase is deposited by physical vapor deposition (PVD) on the surface of metal, which is a vapor phase of chromium and nitrogen atoms in a high vacuum state in a gaseous state. By simultaneously reacting with a metal surface to form a chromium nitride (CrN) phase on the surface of the material in the form of a thin film, there are HCD method, magnetron sputtering method, reactive ion plating method, cathodic arc evaporation method and the like.
상기와 같은 물리적 기상 증착법(PVD)을 이용하여 증착된 질화크롬(CrN) 층은 대부분의 경우에 코팅층이 모재와 다른 물질이고 박막이기 때문에 모재와의 밀착력이 문제가 될 뿐 아니라, 코팅된 제품을 사용온도의 변화가 심한 환경에서 사용할 경우 열팽창 계수의 차이에 의해서 코팅층의 박리가 일어나는 문제점이 있었다.The chromium nitride (CrN) layer deposited using the above physical vapor deposition method (PVD) is in most cases a coating material is different from the base material and is a thin film, not only the adhesion to the base material is a problem, but also the coated product When used in an environment where the use temperature is severely changed, there is a problem that peeling of the coating layer occurs due to a difference in thermal expansion coefficient.
또한, 기상 발생원과 일직선상에 있는 부분만이 처리가 가능하기 때문에 피코팅 제품의 형상에 제한을 받으며, 기상 증착이므로 막의 두께에 한계가 있어서 박막의 수준을 벗어나기 어려워 제품의 응용에 문제점이 있었을 뿐만 아니라, 기본적으로 금속의 증기를 만들기 위해서는 고진공 상태를 유지해야 하므로, 그에 따라 장비가 복잡해질 뿐만 아니라 가격을 상승시키는 등의 문제점이 있었다.In addition, since only the part that is in line with the gas generator can be processed, the shape of the product to be coated is limited, and because of vapor deposition, there is a limitation in the thickness of the film, which makes it difficult to escape the level of the thin film. In addition, basically to maintain the high vacuum in order to make the vapor of the metal, accordingly, there is a problem such as not only complicated equipment, but also increase the price.
따라서, 본 발명은 상기의 문제점들을 해결하기 위하여 이루어진 것으로써, 본 발명의 목적은 간단한 설비를 이용하여 크롬원소와 질소원소를 각각 확산시키는 크로마이징(chromizing)과 이온 질화에 의해 질화크롬(CrN) 상(相)을 형성시키는 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법을 제공하는데 있다.Accordingly, the present invention has been made to solve the above problems, and an object of the present invention is to provide chromium nitride (CrN) by chromizing and ion nitriding to diffuse chromium and nitrogen elements using simple equipment, respectively. The present invention provides a metal surface treatment method by chromizing and ion nitriding to form a phase.
본 발명의 다른 목적은 질화크롬(CrN) 상(相)의 형성 방법이 단순하고 전면에 대해서 처리가 용이하며 확산에 의해 모재표면의 조성이 변하면서 코팅층을 형성하기 때문에 처리 온도와 시간에 따라 두꺼운 코팅층을 얻을 수 있을 뿐만 아니라 온도 변화가 심한 환경에서도 층의 박리가 일어나지 않는 크로마이징 (chromizing)과 이온질화처리에 의한 금속표면처리방법을 제공하는데 있다.It is another object of the present invention that the method of forming a chromium nitride (CrN) phase is simple, and is easy to process on the entire surface. To provide a coating layer as well as to provide a metal surface treatment method by chromizing and ion nitriding treatment in which the layer is not peeled off even in a severe temperature change environment.
본 발명의 또 다른 목적은 제품의 형상에 영향을 거의 받지 않고 표면 처리가 가능하며 종래의 방법에 비해 저렴한 가격으로 처리가 가능한 크로마이징 (chromizing)과 이온질화처리에 의한 금속표면처리방법을 제공하는데 있다.It is still another object of the present invention to provide a metal surface treatment method by chromizing and ion nitriding treatment which can be treated without affecting the shape of the product and can be treated at a lower price than the conventional method. have.
본 발명의 또 다른 목적은 고온에서 안정한 질화크롬(CrN) 상(相)에 의해 우수한 고온 내산화 특성을 얻을 수 있음과 동시에, 우수한 고온 내마모 특성을 얻을 수 있는 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법을 제공하는데 있다.Still another object of the present invention is to obtain excellent high temperature oxidation resistance by chromium nitride (CrN) phase which is stable at high temperature, and to achieve excellent high temperature wear resistance chromizing and ion nitriding. It is to provide a metal surface treatment method by treatment.
도 1은 본 발명의 일 실시예인 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법을 나타낸 플로우챠트,1 is a flowchart showing a metal surface treatment method by chromizing and ion nitriding treatment according to an embodiment of the present invention;
도 2는 본 발명의 일실시예에 의하여 처리된 질화크롬(CrN)층을 나타내는 단면도,2 is a cross-sectional view showing a chromium nitride (CrN) layer treated according to an embodiment of the present invention;
도 3은 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬(CrN) 층의 단면에 대한 크롬과 질소의 EDS(energy dispersive spectroscopy) 선 분포도,3 is an energy dispersive spectroscopy (EDS) line distribution diagram of chromium and nitrogen with respect to a cross section of a chromium nitride (CrN) layer formed on a surface of a sample according to one embodiment of the present invention;
도 4는 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬(CrN)층의 X선회절 분석결과를 나타내는 도면,4 is a view showing the results of X-ray diffraction analysis of the chromium nitride (CrN) layer formed on the surface of the sample according to an embodiment of the present invention,
도 5는 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬(CrN)층의 단면미소 경도분포도.5 is a cross-sectional fine hardness distribution of the chromium nitride (CrN) layer formed on the surface of the sample according to an embodiment of the present invention.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
1 : 복합층 2 : 크롬확산층1: Composite Layer 2: Chromium Diffusion Layer
3 : 모재3: base material
상기 목적을 달성하기 위하여 본 발명의 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법은 시료의 표면을 크롬으로 처리하는 크로마이징 (chromizing)단계와, 상기 크롬처리된 시료의 표면을 질소이온으로 질화처리하는 이온질화처리단계로 이루어지는 것을 특징으로 한다.In order to achieve the above object, the metal surface treatment method of chromizing and ion nitriding treatment of the present invention comprises a chromizing step of treating the surface of the sample with chromium and nitrogen on the surface of the chromium treated sample. It is characterized by consisting of an ion nitriding treatment step of nitriding with ions.
특히, 상기 크로마이징(chromizing)단계는 시료의 표면조도를 적어도 10㎛이상 연마 후 적어도 10분 이상 아세톤으로 초음파 세척하는 시료세척단계와, 최대 50 중량%의 크롬분말, 최대 50 중량%의 염화암모늄(NH4Cl)분말 및 나머지 중량%의 산화알루미늄(Al2O3)분말을 산화알루미늄(Al2O3) 볼을 사용하여 볼믹싱(ball mixing)하여 혼합분말을 제조한 후 상기 혼합분말이 담긴 팩용기에 세척된 시료를 장입하는 분말제조 및 시료장입단계와, 상기 시료가 장입된 팩용기와 티타늄(Ti)을 담은 용기를 온도범위가 1000 내지 1300℃이고 유량이 적어도 200cc/min 인 불활성 또는 환원 분위기에서 1 내지 10시간동안 처리하는 고온처리단계로 이루어지는 것을 특징으로 한다.In particular, the chromizing step is a sample washing step of ultrasonically washing with acetone for at least 10 minutes after polishing the surface roughness of the sample at least 10㎛, and up to 50% by weight of chromium powder, up to 50% by weight of ammonium chloride (NH 4 Cl) powder and the remaining weight% aluminum oxide (Al 2 O 3 ) powder by ball mixing (aluminum oxide (Al 2 O 3 ) ball) using a ball to prepare a mixed powder and then the mixed powder Powder manufacturing and sample loading step of loading the sample washed in the packed container, and the pack container and the container containing titanium (Ti) loaded with the sample inert temperature range of 1000 to 1300 ℃ and flow rate of at least 200cc / min Or a high temperature treatment step of treating for 1 to 10 hours in a reducing atmosphere.
또한 특히, 이온질화처리단계는 상기 크로마이징(chromizing)단계를 거치면서 크롬처리된 시료의 표면조도를 적어도 10㎛까지 연마 후 아세톤으로 적어도 10분이상 초음파 세척하는 시료세척단계와, 상기 세척된 시료를 플라즈마(plasma) 반응챔버내에 장입한 후에 상기 반응챔버내에 수소플라즈마를 발생시켜 적어도 30분이상 스퍼터링(sputtering)시키는 스퍼터링단계와, 상기 반응 챔버 내에 수소와 질소로 구성된 플라즈마를 발생시켜 질소와 수소의 혼합비율이 1:1 내지 1:3, 압력이 1.8 내지 2torr, 바이어스 전압이 직류 500 내지 600V, 그리고 온도가 450 내지 650℃인 상태에서 상기 시료를 처리하는 시료처리단계와, 이온질화처리가 끝난 상기 시료를 질소분위기의 상기 반응챔버내에서 냉각시키는 시료냉각단계로 이루어져 있는 것을 특징으로 한다.In particular, the ion nitriding step is a sample washing step of grinding the surface roughness of the chromium-treated sample to at least 10 ㎛ while performing the chromizing step and ultrasonic cleaning with acetone for at least 10 minutes, and the washed sample Is introduced into a plasma reaction chamber, and a sputtering step of sputtering at least 30 minutes by generating hydrogen plasma in the reaction chamber, and generating a plasma composed of hydrogen and nitrogen in the reaction chamber to generate nitrogen and hydrogen. A sample processing step of processing the sample at a mixing ratio of 1: 1 to 1: 3, a pressure of 1.8 to 2 torr, a bias voltage of 500 to 600 V, and a temperature of 450 to 650 ° C., and ion nitridation treatment. And a sample cooling step of cooling the sample in the reaction chamber of a nitrogen atmosphere.
이하, 크로마이징(chromizing)처리 후 이온질화처리를 실시하는 것을 '복합처리'라 하고, 그렇게 하여 형성된 층을 '복합처리층' 또는 '질화크롬(CrN) 층'이라 한다.Hereinafter, the ion nitriding treatment after chromizing treatment is referred to as a 'composite treatment', and the layer thus formed is referred to as a 'composite treatment layer' or 'chromium nitride (CrN) layer'.
이하, 본 발명의 일 실시예인 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법에 대하여 첨부도면을 참조하여 상세히 설명한다.Hereinafter, a method of treating a metal surface by chromizing and ion nitriding, which is an embodiment of the present invention, will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 일 실시예인 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법을 나타낸 플로우챠트이고, 도 2는 본 발명의 일실시예에 의하여 처리된 질화크롬(CrN)층을 나타내는 단면도이고, 도 3은 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬(CrN)층의 단면에 대한 크롬과 질소의 EDS (energy dispersive spectroscopy)선 분포도이고, 도 4는 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬(CrN)층의 X선회절 분석결과를 나타내는 도면이고, 도 5는 본 발명의 일 실시예에 의하여 시료의 표면에 형성된 질화크롬 (CrN)층의 단면미소 경도분포도이다.1 is a flowchart showing a metal surface treatment method by chromizing and ion nitriding, which is an embodiment of the present invention, and FIG. 2 is a chromium nitride (CrN) layer treated by an embodiment of the present invention. Figure 3 is a cross-sectional view, Figure 3 is an energy dispersive spectroscopy (EDS) line distribution of chromium and nitrogen with respect to the cross section of the chromium nitride (CrN) layer formed on the surface of the sample according to an embodiment of the present invention, Figure 4 is X-ray diffraction analysis of the chromium nitride (CrN) layer formed on the surface of the sample according to an embodiment, Figure 5 is a chromium nitride (CrN) layer formed on the surface of the sample according to an embodiment of the present invention A cross-sectional fine hardness distribution diagram.
본 발명의 일 실시예인 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법은 종래의 방법과는 달리 시료의 표면에 크롬과 질소를 동시에 반응시키지 않고, 먼저 크롬으로 처리하는 크로마이징(chromizing)단계(S1)와, 다음에 상기 크롬처리된 시료의 표면을 다시 질소이온으로 질화처리하는 이온질화처리단계 (S2)의 두 단계로 이루어져 있다.According to an embodiment of the present invention, a metal surface treatment method using chromizing and ion nitriding treatment does not simultaneously react chromium and nitrogen on the surface of a sample, unlike chromizing and ion nitriding. ) Step (S1), and then ion nitride treatment step (S2) of nitriding the surface of the chrome treated sample again with nitrogen ions.
상기 크로마이징(chromizing)단계(S1)는 시료세척단계(S11), 분말제조 및 시료장입단계(S12), 그리고 고온처리단계(S13)의 3단계로 이루어져 있으며, 각각의 단계를 상세히 설명하면 다음과 같다.The chromizing step (S1) is composed of three steps of the sample washing step (S11), powder production and sample loading step (S12), and the high temperature treatment step (S13), each of which will be described in detail Same as
상기 시료세척단계(S11)에서는 시료의 표면조도반경이 적어도 10㎛이하로 될 때까지 연마한 후, 적어도 10분 이상 아세톤으로 초음파 세척한다.In the sample washing step (S11), after polishing until the surface roughness radius of the sample is at least 10㎛ or less, ultrasonic cleaning with acetone for at least 10 minutes.
상기분말제조 및 시료장입단계(S12)에서는 코팅 원료인 최대 50 중량%의 크롬분말과, 활성제인 최대 50 중량%의 염화암모늄(NH4Cl)분말과, 그리고 분말의 소결을 방지하기 위해서 첨가하는 나머지 중량%의 산화알루미늄(Al2O3)분말을 산화알루미늄(Al2O3) 볼(ball)을 사용하여 볼믹싱(ball mixing)하여 혼합분말을 제조한 후, 혼합분말이 담긴 팩용기에 시료 전체가 완전히 잠기도록 세척된 시료를 장입시킨다.In the powder preparation and sample loading step (S12), up to 50% by weight of chromium powder as a coating material, up to 50% by weight of ammonium chloride (NH 4 Cl) powder as an activator, and added to prevent sintering of the powder After mixing the remaining weight percent aluminum oxide (Al 2 O 3 ) powder by using aluminum oxide (Al 2 O 3 ) ball (ball) to prepare a mixed powder, and then in a pack container containing the mixed powder Charge the washed sample so that the entire sample is completely submerged.
상기 고온처리단계(S13)에서는 상기 시료가 장입된 팩용기와 반응로내 산화를 방지하기 위한 티타늄(Ti)을 담은 용기를 온도범위가 1000 내지 1300℃이고 유량이 적어도 200cc/min 인 불활성 또는 환원 분위기에서 1 내지 10시간 동안 처리한다.In the high temperature treatment step (S13), the inert or reducing the pack container in which the sample is loaded and the container containing titanium (Ti) to prevent oxidation in the reactor are in a temperature range of 1000 to 1300 ° C. and a flow rate of at least 200 cc / min. Treatment is carried out in an atmosphere for 1 to 10 hours.
또한, 상기 이온질화처리단계(S2)는 시료세척단계(S21), 스퍼터링단계(S22), 시료처리단계(S23), 그리고 시료냉각단계(S24)의 4단계로 이루어져 있으며, 각각의 단계를 상세히 설명하면 다음과 같다.In addition, the ion nitriding treatment step (S2) is composed of four steps of sample washing step (S21), sputtering step (S22), sample processing step (S23), and sample cooling step (S24), each step in detail The explanation is as follows.
상기 시료세척단계(S21)에서는 상기 크로마이징(chromizing)단계를 거치면서 크롬처리된 시료의 표면조도를 적어도 10㎛까지 연마 후, 아세톤으로 적어도 10분 이상 초음파 세척한다.In the sample washing step S21, the surface roughness of the chromium-treated sample is polished to at least 10 μm while undergoing the chromizing step, followed by ultrasonic cleaning with acetone for at least 10 minutes.
상기 스퍼터링단계(S22)에서는 세척된 시료를 플라즈마(plasma) 반응챔버내에 장입한 후에 상기 반응챔버내에 수소플라즈마를 발생시켜 적어도 30분간 스퍼터링(sputtering)시킨다.In the sputtering step (S22), the washed sample is charged into a plasma reaction chamber, and then hydrogen plasma is generated in the reaction chamber to sputter for at least 30 minutes.
상기 시료처리단계(S23)는 상기 반응 챔버 내에 수소와 질소로 구성된 플라즈마를 발생시켜 질소와 수소의 혼합비율이 1:1 내지 1:3, 압력이 1.8 내지 2torr, 바이어스 전압이 직류 500 내지 600V, 그리고 온도가 450 내지 650℃인 상태에서 상기 시료를 처리한다.The sample processing step (S23) generates a plasma composed of hydrogen and nitrogen in the reaction chamber, the mixing ratio of nitrogen and hydrogen is 1: 1 to 1: 3, the pressure is 1.8 to 2torr, the bias voltage is 500 to 600V DC, And the sample is processed in the state of temperature 450-650 degreeC.
상기 시료냉각단계(S24)에서는 이온질화처리가 끝난 상기 시료를 질소분위기의 상기 반응챔버내에서 냉각시킨다.In the sample cooling step (S24), the sample after the ion nitriding treatment is cooled in the reaction chamber in a nitrogen atmosphere.
상기와 같이 구성된 본 발명의 일 실시예인 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법의 작용을 설명하면 다음과 같다.Referring to the operation of the metal surface treatment method by chromizing and ion nitriding treatment of an embodiment of the present invention configured as described above are as follows.
도 2는 본 발명의 일 실시예의 공정에 따라 처리하여 시료의 표면에 형성시킨 질화크롬(CrN)층의 미세조직단면을 나타내고 있는데, 도면으로부터 알 수 있는 바와 같이 크로마이징(chromizing)에 의하여 최대 300㎛ 두께의 크롬확산층(2)이 형성되었고, 이온질화처리를 실시하여 표면에 약 30 내지 100㎛두께의 복합층(1)이 형성되었다.FIG. 2 illustrates a microstructure cross section of a chromium nitride (CrN) layer formed on a surface of a sample by treatment according to an embodiment of the present invention. As can be seen from the drawing, the maximum thickness is 300 by chromizing. A chromium diffusion layer 2 having a thickness of µm was formed, and the composite layer 1 having a thickness of about 30 to 100 µm was formed on the surface by performing ion nitridation treatment.
도 3은 크로마이징(chromizing)과 이온질화처리한 시료에 대한 EDS(energy dispersive spectroscopy)선 프로파일의 분석결과를 나타낸 도면으로서, 모재(3)위에 크롬의 확산을 확인할 수 있으며 크로마이징(chromizing) 후의 이온질화처리에 의해 질소가 확산되었음을 확인할 수 있다. 또한 도4는 복합처리에 의해 형성된 상 (相)의 X선회절 분석결과를 나타내고 있는데, 시료의 표면에 철계 질화물인 Fe2-3N, Fe4N 등과 함께 질화크롬(CrN) 상(相)이 생성되었음을 보여준다.3 is a diagram showing the results of analysis of the energy dispersive spectroscopy (EDS) line profile for the samples subjected to chromizing and ion nitridation, in which the diffusion of chromium on the base material 3 can be confirmed and after chromizing It can be confirmed that nitrogen was diffused by the ion nitriding treatment. Fig. 4 also shows the results of X-ray diffraction analysis of the phase formed by the complex treatment, with the chromium nitride (CrN) phase together with Fe 2-3 N, Fe 4 N, etc., which are iron nitrides, on the surface of the sample. Shows that it was created.
물리적 기상 증착법(PVD)에 의한 질화크롬(CrN) 박막은 증발된 크롬원자와 질소원자가 화합물을 형성하여 시편 표면에 증착하여 형성된다고 할 수 있지만, 본 발명에서 사용한 복합처리방법에서는 질소원자가 직접 시편과 충돌하여 철계 질화물과 질화크롬(CrN) 상(相)을 형성한다.The chromium nitride (CrN) thin film by physical vapor deposition (PVD) may be formed by evaporating chromium atoms and nitrogen atoms to form a compound and depositing them on the surface of the specimen. Collisions form iron nitride and chromium nitride (CrN) phases.
도 5는 복합처리를 실시하여 단면의 경도분포를 마이크로비커스(micro vickers) 경도측정기를 이용하여 표면으로부터의 깊이에 따라서 측정한 결과이다. 물리적 기상 증착법(PVD)에 의한 CrNx 코팅층의 표면경도는 1600 내지 2000Hv로 보고되었으나, 본 발명의 복합처리에 의해 형성된 표면층의 경도는 1400 내지 1500Hv로서 200 내지 500Hv 정도 낮은 값을 나타내고 있다. 이것은 복합처리에 의해 형성된 표면층이 철계 질화물과 질화크롬(CrN)화합물의 혼합상이기 때문으로 판단할 수 있다.5 is a result of measuring the hardness distribution of the cross section according to the depth from the surface by using a micro vickers hardness tester by performing a composite process. Although the surface hardness of the CrNx coating layer by physical vapor deposition (PVD) has been reported to be 1600 to 2000 Hv, the hardness of the surface layer formed by the composite treatment of the present invention is 1400 to 1500 Hv, which is about 200 to 500 Hv. This can be judged because the surface layer formed by the composite treatment is a mixed phase of iron-based nitride and chromium nitride (CrN) compound.
따라서, 본 발명의 일 실시예에 의하여 니켈이나 철계 합금의 표면에 크로마이징(chromizing)을 실시하여 크롬을 확산시킨 후 이온질화처리를 실시하는 복합처리에 의하면 성공적으로 질화크롬(CrN) 상(相)과 철계 질화물(FexN) 상(相)이 형성된 복합층(1)을 얻을 수 있다.Therefore, according to an embodiment of the present invention, a chromium nitride (CrN) phase is successfully formed by chromizing the surface of nickel or an iron-based alloy to diffuse chromium and then performing ion nitridation treatment. ) And an iron nitride (Fe x N) phase can be obtained.
이상에서 설명한 바와 같이 본 발명의 크로마이징(chromizing)과 이온질화처리에 의한 금속표면처리방법에 의하면, 질화크롬(CrN) 상(相)의 형성 방법이 단순하고 전면에 대해서 처리가 용이한 장점이 있으며, 확산에 의해 모재표면의 조성이 변하면서 코팅층을 형성하기 때문에 처리 온도와 시간에 따라 두꺼운 코팅층을 얻을 수 있을 뿐만 아니라 온도 변화가 심한 환경에서도 층의 박리가 일어나지 않는다. 또한, 제품의 형상에 영향을 거의 받지 않고 표면 처리가 가능하며 질화크롬 (CrN) 상(相)을 형성시키는 종래의 방법에 비해 저렴한 가격으로 처리가 가능하다.As described above, according to the metal surface treatment method by chromizing and ion nitriding treatment of the present invention, the method of forming a chromium nitride (CrN) phase is simple and it is easy to treat the entire surface. In addition, since the coating layer is formed while the composition of the base material surface is changed by diffusion, not only a thick coating layer can be obtained according to the processing temperature and time, but also no peeling of the layer occurs even in an environment where temperature changes are severe. In addition, the surface treatment is possible without being affected by the shape of the product, and the treatment is possible at a lower cost than the conventional method of forming a chromium nitride (CrN) phase.
그리고, 고온에서 안정한 질화크롬(CrN) 상(相)에 의해 우수한 고온 내산화 특성을 얻을 수 있음과 동시에, 우수한 고온 내마모 특성을 얻을 수 있는 효과가 있다.In addition, an excellent high temperature oxidation resistance can be obtained by the chromium nitride (CrN) phase stable at high temperature, and an excellent high temperature wear resistance can be obtained.
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| SU495391A1 (en) * | 1974-04-26 | 1975-12-15 | Рязанский Филиал Государственного Проектно-Технологического И Экспериментального Института "Оргстанкинпром" | Suspension for electroplating parts |
| JPH01234556A (en) * | 1988-03-15 | 1989-09-19 | Sumitomo Metal Ind Ltd | Chromized steel pipe and its production |
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| SU495391A1 (en) * | 1974-04-26 | 1975-12-15 | Рязанский Филиал Государственного Проектно-Технологического И Экспериментального Института "Оргстанкинпром" | Suspension for electroplating parts |
| JPH01234556A (en) * | 1988-03-15 | 1989-09-19 | Sumitomo Metal Ind Ltd | Chromized steel pipe and its production |
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