KR20240088195A - Manufacturing method of TiCrN coating film with improved corrosion resistance - Google Patents
Manufacturing method of TiCrN coating film with improved corrosion resistance Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 70
- 238000005260 corrosion Methods 0.000 title claims abstract description 34
- 230000007797 corrosion Effects 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 32
- 238000009616 inductively coupled plasma Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims description 28
- 229910010169 TiCr Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007789 gas Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000007373 indentation Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004629 contact atomic force microscopy Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
Abstract
본 발명은 내부식성이 향상된 TiCrN 코팅막의 제조방법에 관한 것으로, 보다 구체적으로는 유도결합 플라즈마 마그네트론 스퍼터링 또는 중주파 마그네트론 스퍼터링을 통해 최적의 조건으로 TiCrN 코팅막을 형성하여, 기계적 물성과 내부식성이 우수한 코팅막을 제조할 수 있는 TiCrN 코팅막의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a TiCrN coating film with improved corrosion resistance. More specifically, the TiCrN coating film is formed under optimal conditions through inductively coupled plasma magnetron sputtering or mid-frequency magnetron sputtering to produce a coating film with excellent mechanical properties and corrosion resistance. It relates to a manufacturing method of a TiCrN coating film that can be manufactured.
Description
본 발명은 내부식성이 향상된 TiCrN 코팅막의 제조방법에 관한 것으로, 보다 구체적으로는 유도결합 플라즈마 마그네트론 스퍼터링 또는 중주파 마그네트론 스퍼터링을 통해 TiCrN 코팅막을 형성하여, 기계적 물성과 내부식성이 우수한 코팅막을 제조할 수 있는 TiCrN 코팅막의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a TiCrN coating film with improved corrosion resistance. More specifically, the TiCrN coating film is formed through inductively coupled plasma magnetron sputtering or mid-frequency magnetron sputtering to produce a coating film with excellent mechanical properties and corrosion resistance. It relates to a method of manufacturing a TiCrN coating film.
일반적으로, TiN 및 CrN과 같은 2성분계 금속 질화물 코팅은 높은 경도, 낮은 마찰 계수 및 가혹한 환경에서도 기계 부품의 수명을 연장하는 능력 때문에 여러 산업에서 보호용 코팅으로 현재 사용되고 있다.In general, binary metal nitride coatings such as TiN and CrN are currently used as protective coatings in several industries due to their high hardness, low coefficient of friction and ability to extend the life of mechanical components even in harsh environments.
그러나 이러한 질화물 코팅의 성능과 신뢰성은 해수에 대한 내부식성이 필요한 선박용 내부식 코팅과 같은 특정 응용 분야에서 요구 사항을 충족하지 못하고 있다.However, the performance and reliability of these nitride coatings do not meet the requirements in certain applications, such as marine corrosion-resistant coatings that require corrosion resistance to seawater.
따라서, 2성분계가 아닌 3성분계에 대한 내식성 연구가 개발되기 시작되어, TiCrN과 같은 3성분계 금속 질화물 코팅이 주목을 받게 되었다.Accordingly, research on corrosion resistance of three-component systems, rather than two-component systems, began to be developed, and three-component metal nitride coatings such as TiCrN began to receive attention.
이러한 3성분계 물질인 TiCrN은 2성분계 물질인 CrN과 TiN보다 내식성이 더 높다고 보고되고 있으며, 특히 해수에 대한 내부식성 더 뛰어나다고 보고된 바 있다.TiCrN, a three-component material, is reported to have higher corrosion resistance than CrN and TiN, which are two-component materials. In particular, it has been reported to have superior corrosion resistance to seawater.
또한, 기계적 특성 측면에서 TiN 코팅의 경도는 21GPa이고, CrN 코팅의 경도는 19GPa인 반면, TiCrN 화합물 코팅의 경우 TiN 코팅의 경도나 CrN 코팅의 경도보다 높은 것으로 알려졌다.In addition, in terms of mechanical properties, the hardness of the TiN coating is 21 GPa and the hardness of the CrN coating is 19 GPa, while the hardness of the TiCrN compound coating is known to be higher than that of the TiN coating or CrN coating.
하지만, 3성분계 질화물 코팅의 미세구조 및 경도는 플라즈마 이온 플럭스의 에너지와 밀도에 민감하게 영향을 받아 코팅막을 형성하기 어려운 문제점이 있었다.However, the microstructure and hardness of the three-component nitride coating are sensitive to the energy and density of the plasma ion flux, making it difficult to form a coating film.
본 발명은 이러한 문제점을 해결하기 위해 안출된 것으로, 본 발명의 목적은 마그네트론 스퍼터링을 이용하여 TiCrN을 코팅할 수 있는 내부식성이 향상된 TiCrN 코팅막의 제조방법을 제공하기 위한 것이다.The present invention was developed to solve this problem, and the purpose of the present invention is to provide a method of manufacturing a TiCrN coating film with improved corrosion resistance that can coat TiCrN using magnetron sputtering.
또한, 본 발명의 다른 목적은 TiCrN의 코팅막을 형성시 마그네트론 스퍼터링의 최적의 조건을 제공할 수 있는 내부식성이 향상된TiCrN 코팅막의 제조방법을 제공하기 위한 것이다.In addition, another object of the present invention is to provide a method of manufacturing a TiCrN coating film with improved corrosion resistance that can provide optimal conditions for magnetron sputtering when forming a TiCrN coating film.
본 발명의 목적들은 이상에서 언급한 목적들로 제한되지 않으며, 언급되지 않은 또 다른 목적들은 아래의 기재로부터 당업자에게 명확하게 이해될 수 있을 것이다.The objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will be clearly understood by those skilled in the art from the description below.
상기의 목적을 달성하기 위하여 본 발명은 기판을 준비하는 기판 준비 단계, 준비된 상기 기판을 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치의 챔버 내부에 TiCr 타겟과 대향되는 위치로 장착하고, 초고순도의 Ar과 N2가스를 투입하는 가스 투입 단계 및 유도결합 플라즈마 마그네트론 스퍼터링 또는 중주파 마그네트론 스퍼터링을 이용해 상기 기판에 TiCrN 코팅막을 형성하는 TiCrN 코팅막 형성 단계를 포함하는 내부식성이 향상된 TiCrN 코팅막의 제조방법을 제공한다.In order to achieve the above object, the present invention includes a substrate preparation step of preparing a substrate, mounting the prepared substrate in a position opposite to the TiCr target inside the chamber of an inductively coupled plasma magnetron sputtering device or a mid-frequency magnetron sputtering device, and installing the prepared substrate in a position opposite to the TiCr target. A method for manufacturing a TiCrN coating film with improved corrosion resistance is provided, including a gas input step of introducing Ar and N2 gas and a TiCrN coating film forming step of forming a TiCrN coating film on the substrate using inductively coupled plasma magnetron sputtering or mid-frequency magnetron sputtering. .
바람직한 실시예에 있어서, 상기 초고순도의 Ar과 N2 가스의 투입량은 15 내지 25 sccm인 것이 바람직하다.In a preferred embodiment, the input amount of the ultra-high purity Ar and N2 gas is preferably 15 to 25 sccm.
또한, 본 발명에 내부식성이 향상된 TiCrN 코팅막의 제조방법으로 제조된 TiCrN 코팅막을 더 제공한다.In addition, the present invention further provides a TiCrN coating film manufactured by a method of manufacturing a TiCrN coating film with improved corrosion resistance.
본 발명은 다음과 같은 우수한 효과를 가진다.The present invention has the following excellent effects.
본 발명의 내부식성이 향상된 TiCrN 코팅막의 제조방법에 의하면, 마그네트론 스퍼터링을 이용하여, TiCrN 코팅막을 형성함으로써, 기계적 물성을 향상시킬 수 있는 장점을 지닌다.According to the method for manufacturing a TiCrN coating film with improved corrosion resistance of the present invention, the mechanical properties can be improved by forming the TiCrN coating film using magnetron sputtering.
본 발명의 내부식성이 향상된 TiCrN 코팅막의 제조방법에 의하면, TiCrN 코팅막을 최적의 조건으로 형성하여, 내부식성을 향상시킬 수 있는 장점을 지닌다.According to the method for manufacturing a TiCrN coating film with improved corrosion resistance of the present invention, the TiCrN coating film can be formed under optimal conditions and has the advantage of improving corrosion resistance.
도 1은 본 발명에 따른 내부식성이 향상된 TiCrN 코팅막의 제조방법을 설명하기 위한 단계도이다.
도 2는 본 발명의 비교예, 실시예 1 및 실시예 2에서 각각 제조된 TiCrN 코팅막의 표면거칠기 이미지이다.
도 3은 본 발명의 의 비교예, 실시예 1 및 실시예 2에서 각각 제조된 TiCrN 코팅막의 표면거칠기를 확인한 그래프이다.
도 4는 본 발명의 비교예, 실시예 1 및 실시예 2에서 각각 제조된 TiCrN 코팅막의 나노경도와 탄성률을 확인한 그래프이다.
도 5는 본 발명의 비교예, 실시예 1 및 실시예 2에서 각각 제조된 TiCrN 코팅막의 동전위 분극 실험을 확인한 그래프이다.Figure 1 is a step diagram for explaining a method of manufacturing a TiCrN coating film with improved corrosion resistance according to the present invention.
Figure 2 is an image of the surface roughness of the TiCrN coating film prepared in Comparative Example, Example 1, and Example 2 of the present invention, respectively.
Figure 3 is a graph confirming the surface roughness of the TiCrN coating film prepared in Comparative Example, Example 1, and Example 2 of the present invention, respectively.
Figure 4 is a graph confirming the nanohardness and elastic modulus of the TiCrN coating film prepared in Comparative Example, Example 1, and Example 2 of the present invention, respectively.
Figure 5 is a graph confirming the electropotential polarization experiment of the TiCrN coating film prepared in Comparative Example, Example 1, and Example 2 of the present invention, respectively.
본 발명에서 사용되는 용어는 가능한 현재 널리 사용되는 일반적인 용어를 선택하였으나, 특정한 경우는 출원인이 임의로 선정한 용어도 있는데 이 경우에는 단순한 용어의 명칭이 아닌 발명의 상세한 설명 부분에 기재되거나 사용된 의미를 고려하여 그 의미가 파악되어야 할 것이다.The terms used in the present invention are general terms that are currently widely used as much as possible, but in certain cases, there are terms arbitrarily selected by the applicant. In this case, the meaning described or used in the detailed description of the invention rather than the simple name of the term is considered. Therefore, its meaning must be understood.
이하, 첨부한 도면에 도시된 바람직한 실시예들을 참조하여 본 발명의 기술적 구성을 상세하게 설명한다.Hereinafter, the technical configuration of the present invention will be described in detail with reference to preferred embodiments shown in the attached drawings.
그러나, 본 발명은 여기서 설명되는 실시예에 한정되지 않고 다른 형태로 구체화 될 수도 있다. 명세서 전체에 걸쳐 동일한 참조번호는 동일한 구성요소를 나타낸다.However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like reference numerals refer to like elements throughout the specification.
도 1은 본 발명에 따른 내부식성이 향상된 TiCrN 코팅막의 제조방법을 설명하기 위한 단계도로, 본 발명의 일 실시예에 따른 내부식성이 향상된 TiCrN 코팅막의 제조방법은 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링의 플라즈마에 의해, TiCrN 코팅막을 형성하기 위한 TiCrN 코팅막 제조방법으로, 먼저 기판을 준비하는 기판 준비 단계(S100)가 수행된다.1 is a step diagram illustrating a method for manufacturing a TiCrN coating film with improved corrosion resistance according to the present invention. The method for manufacturing a TiCrN coating film with improved corrosion resistance according to an embodiment of the present invention is an inductively coupled plasma magnetron sputtering device or a mid-frequency wave. In a TiCrN coating film manufacturing method for forming a TiCrN coating film by plasma of magnetron sputtering, a substrate preparation step (S100) is first performed to prepare a substrate.
여기서, 상기 기판은 Si기판이 이용될 수 있다.Here, the substrate may be a Si substrate.
또한, 상기 기판 표면의 불순물을 제거하기 위하여 아센톤과 에틸 알코올에서 초음파 세척을 실시할 수 있다.Additionally, ultrasonic cleaning may be performed in acentone and ethyl alcohol to remove impurities from the surface of the substrate.
다음, 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치의 챔버 내부로 초고순도의 Ar과 N2 가스를 투입하는 가스 투입 단계(S200)가 수행된다.Next, a gas injection step (S200) is performed in which ultra-high purity Ar and N2 gas are introduced into the chamber of the inductively coupled plasma magnetron sputtering device or the mid-frequency magnetron sputtering device.
이때, 상기 Ar과 N2 가스를 투입하기 전 상기 기판과 상기 타겟의 표면에 흡착된 불순물을 제거하기 위해 고순도 Ar 플라즈마를 발생시키는 것이 바람직하다.At this time, it is desirable to generate high-purity Ar plasma to remove impurities adsorbed on the surfaces of the substrate and the target before introducing the Ar and N2 gases.
또한, 상기 챔버 내부로 투입되는 Ar과 N2 가스의 투입량은 15 내지 25sccm인 것이 바람직하다.In addition, it is preferable that the amount of Ar and N2 gas introduced into the chamber is 15 to 25 sccm.
여기서, 상기 기판은 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치의 챔버 내부에 TiCr 타겟과 대향되는 위치로 장착되고, 기판과 TiCr 타겟간의 거리는 60mm로 유지될 수 있다.Here, the substrate is mounted in a position opposite to the TiCr target inside the chamber of the inductively coupled plasma magnetron sputtering device or the mid-frequency magnetron sputtering device, and the distance between the substrate and the TiCr target can be maintained at 60 mm.
이어서, 상기 유도결합 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링을 이용하여 상기 기판에 TiCrN 코팅막을 형성하는 TiCrN 코팅막 형성 단계(S300)가 수행된다.Next, a TiCrN coating film forming step (S300) of forming a TiCrN coating film on the substrate using the inductively coupled plasma magnetron sputtering device or mid-frequency magnetron sputtering is performed.
여기서, 상기 유도결합 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치에 인가되는 전압은 450W 내지 550W인 것이 바람직하다.Here, the voltage applied to the inductively coupled plasma magnetron sputtering device or the mid-frequency magnetron sputtering device is preferably 450W to 550W.
또한, 상기 기판에 TiCrN 코팅막의 균일한 코팅을 위해 상기 기판을 5 내지 15 rpm의 속도로 회전시키는 것이 바람직하다.Additionally, it is preferable to rotate the substrate at a speed of 5 to 15 rpm for uniform coating of the TiCrN coating film on the substrate.
또한, 유도결합 플라즈마 마그네트론 스퍼터링 장치에 인가되는 IPC Power는 75W 내지 125W인 것이 바람직하다.Additionally, the IPC power applied to the inductively coupled plasma magnetron sputtering device is preferably 75W to 125W.
또한, 중주파 마그네트론 스퍼터링 장치에 인가되는 펄스 주파수는 10 내지 20 kHz이고, Duty cycle은 50 내지 95%인 것이 바람직하다.In addition, the pulse frequency applied to the mid-frequency magnetron sputtering device is preferably 10 to 20 kHz, and the duty cycle is preferably 50 to 95%.
비교예Comparative example
먼저, 기판은 Si 기판을 사용하였고, 초음파 세척기를 이용하여 아세톤과 에틸 알코올에서 각각 10분간 초음파 세척을 실시하였다.First, a Si substrate was used, and ultrasonic cleaning was performed in acetone and ethyl alcohol for 10 minutes each using an ultrasonic cleaner.
또한, 기판과 타겟에 고순도 Ar 플라즈마를 발생시켜 세척하였다.Additionally, the substrate and target were cleaned by generating high-purity Ar plasma.
다음, 챔버 내부에 초고순도의 Ar과 N2 가스를 20sccm의 유량으로 투입하였다.Next, ultra-high purity Ar and N2 gases were introduced into the chamber at a flow rate of 20 sccm.
이어서, 상기 직류 마그네트론 스퍼터링 장치에 500W 전압을 인가하여, 상기 기판에 TiCrN 코팅막을 형성하였다.Next, a voltage of 500 W was applied to the DC magnetron sputtering device to form a TiCrN coating film on the substrate.
이때, 코팅시 기판과 타겟 간 거리는 60mm로 유지하였고, 균일한 코팅을 위하여 기판을 10 rpm의 속도로 회전시켰으며, 챔버의 초기 압력은 로터리 펌프와 터보분자 펌프를 사용하여 약 1.4 × 10-4 Torr까지 배기시켰으며, 코팅 중 압력은 (Ar+N2)은 2 mTorr로 유지하였다.At this time, the distance between the substrate and the target during coating was maintained at 60 mm, the substrate was rotated at a speed of 10 rpm for uniform coating, and the initial pressure of the chamber was about 1.4 × 10 -4 using a rotary pump and a turbomolecular pump. The exhaust was exhausted to Torr, and the pressure (Ar+N2) during coating was maintained at 2 mTorr.
실시예 1Example 1
비교예 1과 비교하여, 상기 마그네트론 장치를 중주파 마그네트론 스퍼터링 장치를 사용하였으며, 이때, 펄스 주파수는 15kHz이며, Duty cycle은 75%인 것을 제외하면 동일한 방법을 TiCrN 코팅막을 코팅하였다.Compared to Comparative Example 1, the magnetron device used was a mid-frequency magnetron sputtering device, and the TiCrN coating film was coated in the same manner except that the pulse frequency was 15 kHz and the duty cycle was 75%.
실시예2Example 2
비교예 1과 비교하여, 상기 마그네트론 장치를 유도결합 플라즈마 마그네트론 스퍼터링 장치를 사용하였으며, ICP Power은 500W인 것을 제외하면 동일한 방법을 TiCrN 코팅막을 코팅하였다.Compared to Comparative Example 1, an inductively coupled plasma magnetron sputtering device was used as the magnetron device, and a TiCrN coating film was coated using the same method, except that the ICP power was 500W.
실험예 1(3차원 표면 및 미세구조)Experimental Example 1 (3D surface and microstructure)
비교예, 실시예 1 및 실시예 2의 TiCrN 코팅막을 비 접촉식 AFM 분석을 실시하였으며, 그 결과를 도 2와 도 3에 도시하였다. 도 2와 도 3에 도시된 바와 같이, 비교예, 실시예 1 및 실시예 2에서 코팅된 TiCrN 코팅막의 표면 거칠기는 각각 3.6nm, 3.1nm 및 2.0nm였으며, 비교예와 실시예 2의 TiCrN 코팅막을 비교하면, 스퍼터링 장치에 의해 발생된 에너지 이온은 타겟 표면에서 기판으로 향하는 하전 입자들의 운동에너지를 증가시키고, 기판 표면에 도달한 후에도 표면 이동도를 향상시켜 코팅막 표면의 평탄화가 이루어진 것으로 보이며, 이에 따라 실시예 2에서 코팅된 TiCrN 코팅막의 표면거칠기가 약 44% 관찰된 것을 알 수 있다. Non-contact AFM analysis was performed on the TiCrN coating films of Comparative Example, Example 1, and Example 2, and the results are shown in Figures 2 and 3. As shown in Figures 2 and 3, the surface roughness of the TiCrN coating film coated in Comparative Example, Example 1, and Example 2 was 3.6 nm, 3.1 nm, and 2.0 nm, respectively. Comparing, the energetic ions generated by the sputtering device increase the kinetic energy of the charged particles heading from the target surface to the substrate, and even after reaching the substrate surface, it appears that the surface mobility is improved and the surface of the coating film is flattened. Accordingly, it can be seen that the surface roughness of the TiCrN coating film coated in Example 2 was observed to be about 44%.
실험예 2(나노인덴테이션 경도 및 탄성률)Experimental Example 2 (Nanoindentation hardness and elastic modulus)
비교예, 실시예 1 및 실시예 2의 TiCrN 코팅막을 초정밀 나노인덴테이션 테스트를 이용하여 나노 인덴테이션 경도 및 탄성률을 분석하였으며, 그 결과를 도 4에 도시하였다. 이때, 비교예, 실시예 1 및 실시예 2의 TiCrN 코팅막을 1마이크로터 단위로 30개소 이상의 장소에서 측정된 값을 평균화하였으며, 나노 경도 측정을 위한 입자의 인가 하중은 5 mN으로 고정했으며, 전체 막 두께의 1/10 지점으로 평균화하였다. 도 4에 도시된 바와 같이, TiCrN 코팅막의 나노인덴테이션 경도는 비교예가 13.3GPa, 실시예 1이 18.0GPa, 실시예 2가 26.1GPa 측정되었으며, 탄성률은 비교예가 117.5GPa, 실시예가 1이 140.1 GPa, 실시예 2가 206.8GPa로 측정되었다. 나노인덴테이션 경도와 탄성률 모두 비교예, 실시예 1 및 실시예 2의 순으로 증가한 것을 알 수 있으며, 비교예와 실시예 2를 비교하면, 비교예의 TiCrN 코팅막보다 실시예 2의 TiCrN 코팅막의 나노인덴테이션 경도가 96% 증가하였으며, 탄성률이 76% 증가한 것을 알 수 있었다.The TiCrN coating films of Comparative Examples, Examples 1 and 2 were analyzed for nano-indentation hardness and elastic modulus using ultra-precision nano-indentation tests, and the results are shown in FIG. 4. At this time, the values measured at more than 30 locations for the TiCrN coating films of Comparative Example, Example 1, and Example 2 in units of 1 micrometer were averaged, and the applied load of the particles for measuring nanohardness was fixed at 5 mN, and the overall Averaged at 1/10th of the film thickness. As shown in Figure 4, the nanoindentation hardness of the TiCrN coating film was measured to be 13.3 GPa in Comparative Example, 18.0 GPa in Example 1, and 26.1 GPa in Example 2, and the elastic modulus was 117.5 GPa in Comparative Example and 140.1 GPa in Example 1. GPa, Example 2 was measured at 206.8 GPa. It can be seen that both nanoindentation hardness and elastic modulus increased in the order of Comparative Example, Example 1, and Example 2. When comparing Comparative Example and Example 2, the nano-indentation hardness and elastic modulus of the TiCrN coating film of Example 2 were higher than those of the TiCrN coating film of the Comparative Example. It was found that the indentation hardness increased by 96% and the elastic modulus increased by 76%.
실험예 3(동전위 분극 실험)Experimental Example 3 (Copotential Polarization Experiment)
비교예, 실시예 1, 실시예 2의 TiCrN 코팅막을 동전위 분극 실험을 통해 분식전류밀도와 전위를 분석하였으며, 그 결과를 도 5에 도시하였다. 도 5에 도시된 바와 같이 비교예의 TiCrN 코팅막 부식전위는 -0.145V였으며, 실시예 1의 TiCrN 코팅막 부식전위는 -0.226V였으며, 실시예 2의 TiCrN 코팅막 부식전위는 -0.187V로 실시예 1과 실시예 2의 부식전위가 비교예의 부식전위보다 활성화 되어있음을 알 수 있었다.The TiCrN coating films of Comparative Example, Example 1, and Example 2 were analyzed for corrosion current density and potential through an electropotential polarization experiment, and the results are shown in FIG. 5. As shown in Figure 5, the corrosion potential of the TiCrN coating film of Comparative Example was -0.145V, the corrosion potential of the TiCrN coating film of Example 1 was -0.226V, and the corrosion potential of the TiCrN coating film of Example 2 was -0.187V, which is the same as Example 1. It was found that the corrosion potential of Example 2 was more active than the corrosion potential of Comparative Example.
또한, 비교예의 부식 전류밀도는 2.6×10-6ma/m2였으며, 실시예 1의 부식 전류밀도는 5.3×10-6ma/m2였으며, 실시예 2의 부식 전류밀도는 4.2×10-6ma/m2로 실시예 1과 실시예 2의 코팅막이 비교예의 코팅막보다 내식성이 향상되었음을 알 수 있었다.In addition, the corrosion current density of the comparative example was 2.6×10 -6 ma/m 2 , the corrosion current density of Example 1 was 5.3×10 -6 ma/m 2 , and the corrosion current density of Example 2 was 4.2×10 - At 6 ma/m 2 , it was found that the corrosion resistance of the coating films of Examples 1 and 2 was improved compared to the coating film of the comparative example.
상술한 바와 같이, 본 발명에 따른 내부식성이 향상된 TiCrN 코팅막의 제조방법에 의하면, 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치를 이용하여, TiCrN 코팅막을 형성함으로써, 기재 표면에 기계적 물성과 내부식성이 향상된 코팅막을 코팅할 수 있는 장점을 지닌다.As described above, according to the method for manufacturing a TiCrN coating film with improved corrosion resistance according to the present invention, a TiCrN coating film is formed using an inductively coupled plasma magnetron sputtering device or a mid-frequency magnetron sputtering device, thereby improving mechanical properties and resistance on the surface of the substrate. It has the advantage of being able to coat a coating film with improved corrosivity.
이상에서 살펴본 바와 같이 본 발명은 바람직한 실시예를 들어 도시하고 설명하였으나, 상기한 실시예에 한정되지 아니하며 본 발명의 정신을 벗어나지 않는 범위 내에서 당해 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 다양한 변경과 수정이 가능할 것이다.As discussed above, the present invention has been illustrated and described with reference to preferred embodiments, but it is not limited to the above-described embodiments and is intended to be used by those skilled in the art without departing from the spirit of the invention. Various changes and modifications will be possible.
Claims (3)
준비된 상기 기판을 유도결합형 플라즈마 마그네트론 스퍼터링 장치 또는 중주파 마그네트론 스퍼터링 장치의 챔버 내부에 TiCr 타겟과 대향되는 위치로 장착하고, 초고순도의 Ar과 N2가스를 투입하는 가스 투입 단계; 및
유도결합 플라즈마 마그네트론 스퍼터링 또는 중주파 마그네트론 스퍼터링을 이용해 상기 기판에 TiCrN 코팅막을 형성하는 TiCrN 코팅막 형성 단계를 포함하는 내부식성이 향상된 TiCrN 코팅막의 제조방법.
A substrate preparation step of preparing a substrate;
A gas input step of mounting the prepared substrate in a position opposite to the TiCr target inside the chamber of an inductively coupled plasma magnetron sputtering device or a mid-frequency magnetron sputtering device, and introducing ultra-high purity Ar and N2 gas; and
A method of manufacturing a TiCrN coating film with improved corrosion resistance, comprising forming a TiCrN coating film on the substrate using inductively coupled plasma magnetron sputtering or mid-frequency magnetron sputtering.
상기 초고순도의 Ar과 N2 가스의 투입량은 15 내지 25 sccm인 것을 특징으로 하는 내부식성이 향상된 TiCrN 코팅막의 제조방법
According to clause 1,
Method for producing a TiCrN coating film with improved corrosion resistance, characterized in that the input amount of ultra-high purity Ar and N2 gas is 15 to 25 sccm.
Publications (1)
| Publication Number | Publication Date |
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| KR20240088195A true KR20240088195A (en) | 2024-06-20 |
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