• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2016.11a
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• pp.100-100
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• 2016

물리기상증착방법 (Physical vapor deposition)에 의하여 합성된 천이금속 질화물 박막은 경도, 내마모성 등 절삭공구의 성능을 향상시키며, Ti-Al-N, Ti-Zr-N, Zr-Al-N, Cr-Si-N 등의 3원계 경질 박막에 대한 연구가 지속적으로 이루어지고 있다. 이중에서도 CrAlN 코팅은 높은 경도, 낮은 표면 조도 등의 우수한 기계적 특성 이외에 고온에서 안정한 합금상 형성으로 인하여 우수한 내열성을 보유하여 공구 코팅으로의 적용 가능성이 크다. 그러나 최근 공구사용 환경의 가혹화로 인하여 코팅의 내마모성 및 내열성 등의 물성 향상을 통한 공구의 수명 향상이 필요시 되고 있으며, 코팅에 적합한 중간층을 합성함으로써 공구 코팅으로의 적용 가능성을 높이는 연구들이 진행되고 있다. 본 연구에서는 CrAlN 코팅의 물성을 향상시키기 위해 CrAlN 코팅과 WC-Co 6wt.% 모재 사이에 CrN, CrZrN, CrN/CrZrSiN 등의 다양한 중간층을 합성하였으며, 중간층을 포함한 모든 코팅의 두께는 $3{\mu}m$ 로 제어하였다. 합성된 코팅의 미세조직, 경도 및 탄성계수, 내모성을 분석하기 위해 field emission scanning electron microscopy(FE-SEM), nano-indentation, ball-on-disk 마모시험기 및 ${\alpha}-step$을 사용하였다. 코팅의 내열성을 확인하기 위해 코팅을 furnace에 넣어 공기중에서 500, 600, 700, 800, 900, $1,000^{\circ}C$로 30분 동안 annealing 한 후에 nano-indentation을 사용하여 경도를 측정하였다. CrAlN 코팅을 나노 인덴테이션으로 분석한 결과, 모든 코팅의 경도(35.5-36.2 GPa)와 탄성계수(424.3-429.2 GPa)는 중간층의 종류에 상관없이 비슷한 값을 보인 것으로 확인됐다. 그러나, 코팅의 마찰계수는 중간층의 종류에 따라 다른 값을 보였으며, CrN/CrZrSiN 중간층을 증착한 CrAlN 코팅의 마찰계수는 0.34로 CrZrN 중간층을 증착한 CrAlN 코팅의 마찰계수(0.41)에 비해 낮은 값을 보였다. 또한, 코팅의 마모율 및 마모폭도 비슷한 경향을 보인 것으로 보아, CrN/CrZrSiN 중간층을 합성한 CrAlN 코팅의 내마모성이 상대적으로 우수한 것으로 판단된다. 이것은 중간층의 H/E ratio가 코팅의 내마모성에 미치는 영향에 의한 결과로 사료된다. H/E ratio는 파단시의 최대 탄성 변형율로써, 모재/중간층/코팅의 H/E ratio 구배에 따라 코팅 내의 응력의 완화 정도가 변하게 된다. WC 모재 (H/E=0.040)와 CrAlN 코팅(H/E=0.089) 사이에서 CrN, CrZrSiN 중간층의 H/E ratio 는 각각 0.076, 0.083 으로 모재/중간층/코팅의 H/E ratio 구배가 점차 증가함을 확인 할 수 있었고, 일정 응력이 지속적으로 가해지면서 진행되는 마모시험중에 CrN과 CrZrSiN 중간층이 WC와 CrAlN 코팅 사이에서 코팅 내부의 응력구배를 완화시키는 역할을 함으로써 CrAlN 코팅의 내마모성이 향상된 것으로 판단된다. 모든 코팅을 열처리 후 경도 분석결과, CrN/CrZrSiN 중간층을 증착한 CrAlN 코팅은 $1,000^{\circ}C$까지 약 28GPa의 높은 경도를 유지한 것으로 확인 되었고, 이는 CrZrSiN 중간층 내에 존재하는 $SiN_x$ 비정질상의 우수한 내산화성에 의한 결과로 판단된다.

• Applied Biological Chemistry
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• v.41 no.4
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• pp.241-245
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• 1998

Two oxidation states of chromium commonly occur in natural soil/water systems, Cr(III) and Cr(VI). The oxidized form, Cr(VI), exists as the chromate ion and is more mobile and toxic than Cr(III). Therefore oxidation of Cr(III) by various Mn-oxides in natural systems is a very important environmental concern. Organic substances can inhibit the Cr(III) oxidation by binding, Cr(III) strongly and also by dissolving Mn-oxides. Most of Cr(III) oxidation studies were carried out using in vitro systems without organic substances which exist in natural soil/water systems. In this study effect of organic acids - oxalate and pyruvate - on Cr(III) oxidation by $birnessite({\delta}-MnO_2)$ was examined. The two organic acids significantly inhibited Cr(III) oxidation by birnessite. Oxalate showed more significant inhibition than pyruvate. As solution pH was lowered in the range of 3.0 to 5.0, the Cr(III) oxidation was more strongly depressed. Addition of more organic acids reduced the Cr(III) oxidation mare extensively. Different inhibition effects by the organic acids could be due to their ability of reductive dissolution of Mn-oxides and/or Cr(III) binding. Organic acids dissolved Mn-oxide during the Cr(III) oxidation by the oxide, Dissolution by oxalic acid was much greater than that by pyruvate, and the dissolution was more extensive at lower pH. Inhibition of Cr(III) oxidation was parallel to the dissolution of Mn-oxide by organic acids. Although the effect of Cr(III) binding by organic acids on Cr(III) oxidation is not known yet, Mn-oxide dissolution by organic acids could be a main reason for the inhibition of Cr(III) oxidation by Mn-oxide in presence of organic acids. Thus oxidation of Cr(III) to Cr(VI) by various Mn-oxides in natural systems could be much less than the oxidation estimated by in vitro studies with only Cr(III) and Mn-oxides.

• Analytical Science and Technology
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• v.6 no.2
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• pp.217-223
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• 1993

Thin films of the Au/Cr, Au/Ni/Cr and Au/Pd/Cr systems were deposited on alumina substrates at ambient temperature and $250^{\circ}C$ in a high-vacuum resistance heating evaporator and annealed at $300^{\circ}C$, $450^{\circ}C$ and $600^{\circ}C$ for 1 hour in air, respectively. The film thicknesses of Au, Ni(or pd), and Cr were $1000{\AA}$, $300{\AA}$, and $50{\AA}$, respectively. The substrate temperature during deposition and the post-deposition annealing temperature affected the sheet resistance of thin-films due to the inter-diffusion of each layer. As a result of Auger depth profile analysis, in the Au/Cr system Cr already diffused out to Au surface during deposition at the substrate temperature of $250^{\circ}C$ and Au distribution changed after heat treatment. In the Au/Ni/Cr and Au/Pd/Cr systems, diffusion phenomena of Ni and Pd were found and especially Ni (approximately 45 at.%) diffused out to Au surface and oxidized.

• Journal of the Korean Chemical Society
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• v.43 no.4
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• pp.418-422
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• 1999

A method is described for the selective determination of Cr(III) and Cr(VI) in aqueous solutios by flame atomic absorption spectrometry. Selective extraction of $Cr_2O_7^{2-}$ was performed by Aliquat 336/NIBK from the mixtures of $Cr^{3+}$ and $Cr_2O_7^{2-}$, and the extraction of $Cr^{3+}$ was followed after complex formation with citrate by using the same extractant. The concentraction of each analyte in the extract was determined by $N_2O-C_2H_2$ flame atomic absorption spectrometry. The recoveries of $Cr^{3+}$ and $Cr_2O_7^{2-}$ from 50mL of aqueous solution ranging 0.1~1.0 ${\mu}g/mL$ as Cr respectively by single extractions with 5 mL of 1%(V/V) Aliquat 336/MIBK were resulted as 98.8∼101.7%.

• Journal of the Korean Ceramic Society
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• v.25 no.1
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• pp.35-41
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• 1988

In the system of Li2O-MgO-Al2O3-Cr2O3, the crystalline solid solution of LiCrO2 along the pseudo-binary join between rocksalt structure(LiCrO2) and spinel structure(MgCr2O4 or MgAl2O4) have been investigated by x-ray diffraction techniques. In this study, order-disorder phase transition of LiCrO2 was observed and the unit cell of the disordered LiCrO2 structure has been established. It has been found that LiCrO2 makes a solid solution over a wide range with MgAl2O4, while not with MgCr2O4. This difference was explained as being due to the ability of oxygen lattice distortion which depended on the relative sizes and chemical bonding characteristics of the substituted ions.

• Journal of the Korean institute of surface engineering
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• v.34 no.3
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• pp.231-239
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• 2001

The structure and composition of Cr-nitrides formed on an electroplated hard Cr layer during an ionnitriding process was analyzed, and the growth kinetics of the Cr-nitrides was examined as a function of the ion-nitriding temperature and time in order to establish a computer simulation model prediction the growth behavior of the Cr-nitride layer. The Cr-nitrides formed during the ion-nitriding at $550~770^{\circ}C$ were composed of outer CrN and inner $Cr_2$N layers. A nitrogen diffusion model in the multi-layer based on fixed grid FDM (Finite Difference Method) was applied to simulate the growth kinetics of Cr-nitride layers. By measuring the thickness of each Cr-nitride layer as a function of the ion-nitriding temperature and time, the activation energy for growth of each Cr-nitride was determined; 82.26 KJ/mol for CrN and 83.36 Kj/mol for $Cr_2$N. Further, the nitrogen diffusion constant was determined in each layer; $9.70$\times$10^{-12}$ /$m^2$/s in CrN and $2.46$\times$10^{-12}$ $m^2$/s in $Cr_2$N. The simulation on the growth kinetics of Cr-nitride layers was in good agreements with the experimental results at 550~72$0^{\circ}C$.

• Korean Journal of Materials Research
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• v.11 no.4
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• pp.324-328
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• 2001

CrN films were deposited onto STD61 steel substrates using an arc-ion plating apparatus, with and without ion-nitriding pretreatment, and their oxidation was studied between 700 and $900^{\circ}C$ for 40hr in air. The oxidation behavior was examined by thermogravimetric analyses, X-ray diffraction. EDS and SEM. The deposited CrN films consisted of CrN and $Cr_2$N phases. The CrN films increased the oxidation resistance of the substrate by forming a protective $Cr_2$$O_3$ layer. The ion-nitriding pretreatment has not affected the oxidation resistance of the CrN film.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 1999.10a
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• pp.81-84
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• 1999

The aqueous geochemical characteristics of Cr(III) and Cr(Ⅵ) in environmental systems are very different from one another: Cr(Ⅵ) is highly soluble, mobile and toxic relative to Cr(III) Reduction of Cr(Ⅵ) to Cr(III) are beneficial in aquatic systems because of the transformation of a highly mobile and toxic species to one having a low solubility in water, thus simultaneously decreasing chromium mobility and toxicity. Fe(II) species are excellent reductants for transforming Cr(Ⅵ) to Cr(III), and in addition, keeping Cr(III) concentrations below the drinking water standard of 52 ppb at pH values between 5 and 11. Investigations of the effects of NOM on Cr(Ⅵ) reduction are for examining the feasibility of using ferrous iron to reduce hexavalent chromium in subsurface environments. Experiments in the presence of soils, however, showed that the solid phase consumes some of the reducing capacity of Fe(II) and makes the overall reduction kinetics slower. The soil components bring about consumption of the ferrous iron reductant. Particular attention is devoted to the complexation of Fe(II) by NOM and the subsequent effect on Cr(Ⅵ) reduction. Cr(Ⅵ) reduction rate by Fe(II) was affected by the presence of NOM (humic acid), The effects of humic acid was different from the solution pH values and the concentration of humic acid. It was probably due to the reactions between humic acid and Cr(Ⅵ), humic acid and Fe(II), and between Cr(Ⅵ) and Fe(II), at each pH.

• Journal of Korea Soil Environment Society
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• v.4 no.2
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• pp.11-31
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• 1999

Removal of hexavalent chromium from artificial groundwater (AGW) by granular activated carbon (GAC) was investigated in batch and continuous-flow column studies. Experimental parameters that were examined included solution pH, presence of dissolved oxygen (DO), and GAC pretreatment with Fe(II). As the solution pH increased from 4 to 7.5, the amount of Cr(VI) removed by both GACs decreased significantly. Exclusion of DO from the experimental systems resulted in greater removal of Cr(VI) from solution, possibly as a result of reduction to Cr(III). However, pretreatment of the GAC with a reductant (Fe(II)) did not improve Cr(VI) removal. Equilibration With 0.01 M $K_2$$HPO_4$[to extract adsorbed Cr(VI)] followed by a wash with 0.02 N $K_2$$HPO_4$[to remove precipitated/sorbed Cr(III)] proved to be a viable approach for the regeneration of carbons whose Cr(VI) removal capacities had been exhausted. The performance of the regenerated carbons exceeded that of the virgin carbons, primarily because of the favorable adsorption of Cr(VI) at lower pH values and the reduction of Cr(VI) to Cr(III), The presence of Cr(III) in acid wash solutions provides direct evidence that Cr(VI) is reduced to Cr(III) in GAC systems under relatively acidic conditions. GAC performance over five complete cycles was consistently high, which suggests that such a system will be able to function over many operation cycles without deleterious effects.

• Korean Journal of Materials Research
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• v.8 no.8
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• pp.757-765
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• 1998

This study was performed to investigate the influence of fuel/oxygen ratio (F/O= 3.2, 3.0, 2.8) on the oxidation behavior of two kinds of (20wt%NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$, and 7wt%NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$) composite powder with different manufacturing method. The results show that the oxidation behavior between the 20wt% NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$ and 7wt% NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$ coating was widely different. The surface morphology of the coating composed of 7wt% NiCr mixed $\textrm{Cr}_{3}\textrm{C}_{2}$ was changed to porous with F/O ratio by the aggressive evolution of gas phases($\textrm{CO}_2$, CO and $\textrm{CrO}_3$) and the oxide cluster composed of Ni and Cr were grown after oxidation at $1000^{\circ}C$ for 50 hours. But the surface morphology of the coating composed of 20wt% NiCr claded $\textrm{Cr}_{3}\textrm{C}_{2}$ was not changed to porous after oxidation at $1000^{\circ}C$ for 50 hours. Therefore, the reason for high oxidation rate is due to activation of $\textrm{Cr}_{3}\textrm{C}_{2}$ to oxidation by entrapped oxygen gases within coating layer, and to closely relate with the decomposition of $\textrm{Cr}_{3}\textrm{C}_{2}$ to $\textrm{Cr}_{7}\textrm{C}_{3}$ phase. Accordingly, On the evidence of these results, the study about the oxidation behavoir of the HVOF sprayed $\textrm{Cr}_{3}\textrm{C}_{2}$ coating depending on hydrogen flow rate must be done.