KR20040075207A - ELECTROLYTE FOR NANOCRYSTALLINE Fe-Ni ALLOYS WITH LOW THERMAL EXPANSION AND THE PROCESS OF PRODUCING THE SAME - Google Patents
ELECTROLYTE FOR NANOCRYSTALLINE Fe-Ni ALLOYS WITH LOW THERMAL EXPANSION AND THE PROCESS OF PRODUCING THE SAME Download PDFInfo
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Abstract
Description
본 발명의 목적은 열팽창계수가 9μm/m·K 이하인 저열팽창특성을 갖는 Fe-Ni 합금 박판을 전기도금(전주도금)(electrodeposition) 또는 전주성형(electroforming) 방법을 이용하여 제조할 수 있는 도금(성형)용액과 공정조건을 제공하는 것이다.An object of the present invention is to provide a plating method for producing a Fe-Ni alloy sheet having a low thermal expansion property having a thermal expansion coefficient of 9 μm / m · K or less by using an electroplating or electroforming method. Molding) solution and process conditions.
Fe-Ni합금은 Ni 함량에 따라 다양한 물성을 나타내며, 저열팽창 특성은 Ni의 함량이 중량비로 20%∼50% 범위일 때 나타난다 (D. R. Rancourt, S. Chehab and G. Lamarche, J. Mag. Mag. Mater. 78 (1989) 129 참조). 이 중 인바합금(Invaralloy)이라 불리는 64%Fe-36%Ni 조성의 합금은 열팽창계수가 0에 근접하며, Guillaume이 1897년 처음 발명한 이래 (C. E. Guillaume, C.R. Acad. Sci. Paris 124 (1897) 176 참조) 대표적인 저열팽창 합금으로 생산되어 상업적으로 널리 이용해 오고 있다.Fe-Ni alloys exhibit various properties depending on the Ni content, and low thermal expansion properties occur when the Ni content is in the range of 20% to 50% by weight (DR Rancourt, S. Chehab and G. Lamarche, J. Mag. Mag). Mater. 78 (1989) 129). Among these alloys, 64% Fe-36% Ni, called Invaralloy, have a coefficient of thermal expansion close to zero, and since Guillaume first invented in 1897 (CE Guillaume, CR Acad. Sci. Paris 124 (1897) It is produced as a representative low thermal expansion alloy and has been widely used commercially.
인바합금을 사용하는 한 예로서, TV와 개인용컴퓨터(PC)의 컬러모니터(color monitor)용 음극관(cathode ray tube, CRT)의 필수부품인 섀도우마스크(shadow mask)를 들 수 있다. 섀도우마스크의 역할은 전자총에서 나온 전자빔이 섀도우마스크의 구멍을 통해 형광체에 충돌하도록 유도하는 것이나, 이 과정에서 전체 전자빔의 2/3 정도는 섀도우마스크에 충돌하여 온도를 상승시킨다. 따라서 섀도우마스크의 온도가 상승하더라도 정확한 구멍크기와 형상을 유지하기 위해서는 저열팽창재료, 즉 인바합금을 사용해야만 컬러모니터의 해상력을 획득할 수 있다. CRT뿐만 아니라 최근 개발되고 있는 평면모니터용 FED(field emission display)에서도 인바합금으로 만든 섀도우마스크의 사용이 예상된다.An example of using inva alloys is a shadow mask which is an integral part of a cathode ray tube (CRT) for color monitors in TVs and personal computers (PCs). The role of the shadow mask is to induce an electron beam from the electron gun to impinge the phosphor through the hole of the shadow mask, but in the process, about two thirds of the total electron beam collides with the shadow mask to raise the temperature. Therefore, in order to maintain accurate hole size and shape even when the temperature of the shadow mask increases, the resolution of the color monitor can be obtained only by using a low thermal expansion material, that is, an inva alloy. In addition to CRTs, shadow masks made of inva alloy are expected to be used in field emission displays (FEDs) for flat panel monitors.
저열팽창 Fe-Ni 합금을 사용하는 또 다른 예로서, 집적회로(integrated circuit, IC) 칩(chip)을 지지하는 리드프레임(lead frame)을 들 수 있다. 리드프레임은 칩과 외부를 전기적으로 접속하는 부품인데, 칩에 사용되는 재료와 리드프레임의 열팽창계수가 비슷해야만 열응력을 줄여 IC칩의 수명을 확보할 수 있다. 이 경우 칩의 재료 선택에 따라 Ni함량을 40%∼49%로 변화시킨 Fe-Ni합금을 사용한다. 이 외에도 저열팽창용 Fe-Ni 합금은 Ni 함량을 변화시키면서 바이메탈, 유리/금속밀봉, 전기부품, 내연기관 피스톤 등에 사용되고 있다.Another example of using a low thermal expansion Fe-Ni alloy is a lead frame supporting an integrated circuit (IC) chip. The lead frame is a component that electrically connects the chip and the outside. The thermal expansion coefficient of the lead frame and the material used for the chip are similar to each other to reduce the thermal stress to ensure the life of the IC chip. In this case, a Fe-Ni alloy is used in which the Ni content is changed from 40% to 49% according to the material selection of the chip. In addition, Fe-Ni alloys for low thermal expansion are used in bimetals, glass / metal seals, electrical components, and internal combustion engine pistons with varying Ni content.
상기한 Fe-Ni합금 박판을 제조하는 방법은 여러 가지가 있으나 냉간압연법이 주로 이용되고 있다. 냉간압연법을 사용하는 경우 진공용해, 단조, 열간압연, 노말라이징, 1차냉간압연, 중간어닐링, 2차냉간압연, 환원분위기에서의 최종어닐링 등의 공정을 거쳐야 하며 두께 0.1mm 이하의 인바합금 박판을 제작하기 위해서는 다단 압연을 시행해야 하기 때문에 (미국등록특허 US patent 494834 참조) 공정이 복잡하고 균질의 제품을 얻기 어려울 뿐만 아니라 제조단가가 높다. 뿐만 아니라 공정 중에 개입되는 불순물 및 공정조건의 변화에 열팽창계수가 민감하게 변하는 문제가 있다 (Metals Handbook, 9th ed. Vol. 3, ASM (1980) 889 참조).There are various methods of manufacturing the above Fe-Ni alloy sheet, but cold rolling is mainly used. When cold rolling is used, vacuum melting, forging, hot rolling, normalizing, primary cold rolling, intermediate annealing, secondary cold rolling, and final annealing in a reducing atmosphere are required. In order to manufacture a thin plate, multi-stage rolling must be performed (see US Patent 494834), which is not only difficult to obtain a homogeneous product but also a high manufacturing cost. In addition, there is a problem that the coefficient of thermal expansion is sensitive to changes in impurities and process conditions involved in the process (see Metals Handbook, 9th ed. Vol. 3, ASM (1980) 889).
종래의 제조방법의 한계를 극복하기 위해 최근, 전기도금(성형)에 의한 Fe-Ni 합금제조에 대한 연구가 많이 이루어지고 있으나, 전해액의 배합과 공정조건이 까다롭기 때문에 Ni 함량을 20∼50wt% 함유하는 Fe-Ni 합금의 전주성형에서는 아직까지 바람직한 제품이 제조되지 못하고 있다. 한 예로, 특허출원(출원번호10-2001-0019169)의 도금(성형)액 및 공정조건으로는 퍼멀로이(20%Fe-80%Ni, Permalloy)는 재현성있게 제조되는 반면, 인바 합금 및 Ni 함유량이 50wt%이하인 Fe-Ni 합금 제조를 위해서는 도금(성형)액의 배합과 공정조건의 근본적인 변화가 요망된다.In order to overcome the limitations of the conventional manufacturing method, a lot of researches have recently been made on the production of Fe-Ni alloys by electroplating (molding). However, since the formulation and process conditions of the electrolyte are difficult, it contains 20 to 50 wt% of Ni. In the electroforming of the Fe-Ni alloy, a desirable product has not yet been produced. For example, as a plating solution and process conditions of the patent application (Application No. 10-2001-0019169), Permalloy (20% Fe-80% Ni, Permalloy) is produced reproducibly, while Invar alloy and Ni content For the production of Fe-Ni alloys of less than 50wt%, it is necessary to mix the plating (molding) solution and fundamentally change the process conditions.
본 발명은 상기의 문제점을 극복하기 위해서 제안된 것으로, 소망하는 열팽창계수 값을 갖는 Fe-Ni 합금이 정확한 합금조성을 갖도록 단일공정인 전주성형방법으로 제조하기 위한 도금(성형)액의 조성과 공정조건을 제공함에 그 목적이 있다.The present invention has been proposed to overcome the above problems, and the composition and process conditions of the plating (molding) liquid for producing in a single-step electroforming method so that the Fe-Ni alloy having a desired coefficient of thermal expansion value has an accurate alloy composition The purpose is to provide.
도 1은 본 발명에서 Fe-Ni합금 박판을 제작할 수 있는 전주도금(성형)장치의 개략도이다.Figure 1 is a schematic diagram of the electroplating (molding) apparatus for producing a Fe-Ni alloy sheet in the present invention.
상기한 본 발명의 달성 목적은 다음과 같이 이상적으로 배합된 전해액의 조성과 특정한 공정조건에 의해 정확한 Fe-Ni 합금 조성이 얻어짐으로써 달성된다.The above object of the present invention is achieved by obtaining an accurate Fe-Ni alloy composition by the composition of the ideally formulated electrolyte solution and the specific process conditions.
본 발명에서 제안하는 전해액은 FeSO4·7H2O(Ferrous Sulfate), NiSO4·6H2O(Nickel Sulfate), NiCl2·6H2O(Nickel Chloride), FeCl2·4H2O(Ferrous Chloride)와 Ni(NH2SO3)2(Nickel Sulfamate)을 기본으로 하여 배합하였으며, 붕산(H3BO3, Boric acid) 20∼30g/l 와, 사카린(C7H4NO3SNa, Sodium Saccharin) 1∼3g/l 와 나트륨라우릴설페이트(C12H25O4SNa, Sodium Lauryl Sulfate) 0.1 ∼ 0.3g/l 와, 염화나트륨(NaCl, Sodium Chloride) 20∼40g/l 를 함유한 용액이다. 이 중 붕산(H3BO3, Boric acid)은 22∼25g/l , 사카린(C7H4NO3SNa, Sodium Saccharin)은 2.0∼2,4g/l 와 나트륨라우릴설페이트(C12H25O4SNa, Sodium Lauryl Sulfate) 0.1 ∼ 0.2g/l 와, 염화나트륨(NaCl, Sodium Chloride) 30∼32g/l 를 함유하였을 때가 더 바람직한 효과를 나타낸다고 보여진다. 상기한 철화합물과 니켈화합물은 전해액에서 이온으로 유리된 후, 전주도금(성형)과정에서 Fe-Ni로 전착되며, 붕산은 pH 완충제, 사카린은 도금(성형)재의 응력완화제, 염화나트륨은 전해질의 전도도 향상을 위해 첨가한다. 전주도금(성형) 중에 전해액의 pH는 2∼4 범위로 유지되며, 전류밀도는 50∼100mA/cm2, 전해액 온도는 50∼60℃에서 시행된다.The electrolyte proposed in the present invention is FeSO 4 · 7H 2 O (Ferrous Sulfate), NiSO 4 · 6H 2 O (Nickel Sulfate), NiCl 2 · 6H 2 O (Nickel Chloride), FeCl 2 · 4H 2 O (Ferrous Chloride) And Ni (NH 2 SO 3 ) 2 (Nickel Sulfamate) was used as the basis, and boric acid (H 3 BO 3 , Boric acid) 20-30g / l and saccharin (C 7 H 4 NO 3 SNa, Sodium Saccharin) A solution containing 1 to 3 g / l, sodium lauryl sulfate (C 12 H 25 O 4 SNa, Sodium Lauryl Sulfate) and 0.1 to 0.3 g / l, and sodium chloride (NaCl, Sodium Chloride) 20 to 40 g / l. Among them, boric acid (H 3 BO 3 , Boric acid) is 22-25g / l, saccharin (C 7 H 4 NO 3 SNa, Sodium Saccharin) is 2.0-2,4g / l and sodium lauryl sulfate (C 12 H 25 O 4 SNa, Sodium Lauryl Sulfate) 0.1-0.2 g / l and sodium chloride (NaCl, Sodium Chloride) 30-32 g / l are shown to show more favorable effect. The iron compound and the nickel compound are released as ions in the electrolyte, and then electrodeposited with Fe-Ni during electroplating (molding), boric acid is a pH buffer, saccharin is a stress relaxation agent of plating (molding) material, and sodium chloride is electrolyte conductivity. Add for improvement. During electroplating (molding), the pH of the electrolyte is maintained in the range of 2 to 4, the current density is 50 to 100mA / cm 2 , the temperature of the electrolyte is carried out at 50 to 60 ℃.
상기한 공정조건하에서 Ni 함량이 20∼50wt% 범위의 조성을 갖는 Fe-Ni합금 박판을 전주도금(성형)방법으로 제조하기 위한 도금(성형, 전해)액의 조성을 <표1∼6>에 나타내었다.Table 1-6 shows the composition of the plating (molding and electrolytic) solution for producing a Fe-Ni alloy thin plate having a composition in the range of 20 to 50wt% Ni under the above process conditions. .
<증류수 1liter 기준><1 liter of distilled water>
<증류수 1liter 기준><1 liter of distilled water>
<증류수 1liter 기준><1 liter of distilled water>
<증류수 1liter 기준><1 liter of distilled water>
<증류수 1liter 기준><1 liter of distilled water>
<표1>은 FeSO4·7H2O(Ferrous Sulfate)와 NiSO4·6H2O(Nickel Sulfate)를 도금(성형)액의 주성분으로 사용하였으며, Nickel Sulfate의 양을 97g/l로 일정하게 유지하면서 Ferrous Sulfate의 양을 28∼73g/l 범위에서 변화하여 소망하는 조성의 Fe-Ni합금을 제조한 결과를 (실시예1∼10)에 나타냈다.Table 1 shows that FeSO 4 · 7H 2 O (Ferrous Sulfate) and NiSO 4 · 6H 2 O (Nickel Sulfate) were used as the main components of the plating (molding) solution, and the amount of Nickel Sulfate was kept constant at 97 g / l. While changing the amount of ferrous sulfate in the range of 28 to 73 g / l, Fe-Ni alloys having the desired compositions were shown in (Examples 1 to 10).
<표2>는 FeSO4·7H2O(Ferrous Sulfate)와 NiCl2·6H2O(Nickel Chloride)를 도금(성형)액의 주성분으로 사용하였으며, Nickel Chloride의 양을 97g/l로 일정하게 유지하면서 Ferrous Sulfate의 양을 36∼70g/l 범위에서 변화하여 소망하는 조성의Fe-Ni합금을 제조한 결과를 (실시예11∼17)에 나타냈다.<Table 2> shows FeSO 4 · 7H 2 O (Ferrous Sulfate) and NiCl 2 · 6H 2 O (Nickel Chloride) as the main components of the plating (molding) solution, keeping the amount of Nickel Chloride constant at 97g / l While changing the amount of Ferrous Sulfate in the range of 36 to 70 g / l, Fe-Ni alloys having the desired compositions were shown in (Examples 11 to 17).
<표3>은 FeCl2·4H2O(Ferrous Chloride)와 NiSO4·6H2O(Nickel Sulfate)를 도금(성형)액의 주성분으로 사용하였으며, Nickel Sulfate의 양을 97g/l로 일정하게 유지하면서 Ferrous Chloride의 양을 30∼70g/l 범위에서 변화하여 소망하는 조성의 Fe-Ni합금을 제조한 결과를 (실시예18∼23)에 나타냈다.<Table 3> shows FeCl 2 · 4H 2 O (Ferrous Chloride) and NiSO 4 · 6H 2 O (Nickel Sulfate) as the main components of the plating (molding) solution, and the amount of Nickel Sulfate was kept constant at 97 g / l. While the amount of Ferrous Chloride was varied in the range of 30 to 70 g / l, Fe-Ni alloys having a desired composition were shown in (Examples 18 to 23).
<표4>는 FeCl2·4H2O(Ferrous Chloride)와 NiCl2·6H2O(Nickel Chloride)를 도금(성형)액의 주성분으로 사용하였으며, Nickel Chloride의 양을 97g/l로 일정하게 유지하면서 Ferrous Chloride의양을 34∼65g/l 범위에서 변화하여 소망하는 조성의 Fe-Ni 합금을 제조한 결과를 (실시예24∼29)에 나타냈다.<Table 4> shows FeCl 2 · 4H 2 O (Ferrous Chloride) and NiCl 2 · 6H 2 O (Nickel Chloride) as the main components of the plating (molding) solution, and the amount of Nickel Chloride is kept constant at 97 g / l. The Ferrous Chloride content was varied in the range of 34 to 65 g / l to produce Fe-Ni alloys of the desired compositions.
<표5>는 FeSO4·7H2O(Ferrous Sulfate) 와 Ni(NH2SO3)2(Nickel Sulfamate)를 도금(성형)액의 주성분으로 사용하였으며, Nickel Sulfamate의 양을 97g/l로 일정하게 유지하면서 Ferrous Sulfate의 양을 25∼52g/l 범위에서 변화하여 소망하는 조성의 Fe-Ni 합금을 제조한 결과를 (실시예30∼35)에 나타냈다.<Table 5> shows FeSO 4 · 7H 2 O (Ferrous Sulfate) and Ni (NH 2 SO 3 ) 2 (Nickel Sulfamate) as the main components of the plating (molding) solution, and the amount of Nickel Sulfamate was constant at 97g / l. The results of preparing the Fe-Ni alloy having the desired composition by varying the amount of Ferrous Sulfate in the range of 25 to 52 g / l while maintaining it were shown in (Examples 30 to 35).
<표6>은 FeCl2·4H2O(Ferrous Chloride) 와 Ni(NH2SO3)2(Nickel Sulfamate)를 도금(성형)액의 주성분으로 사용였으며, Nickel Sulfamate의 양을 97g/l로 일정하게 유지하면서 Ferrous Chloride의 양을 22∼52g/l 범위에서 변화하여 소망하는 조성의 Fe-Ni 합금을 제조한 결과를 (실시예36∼41)에 나타냈다.<Table 6> shows the use of FeCl 2 · 4H 2 O (Ferrous Chloride) and Ni (NH 2 SO 3 ) 2 (Nickel Sulfamate) as the main components of the plating (molding) solution, and the amount of Nickel Sulfamate was constant at 97g / l. The results of producing the Fe-Ni alloy of the desired composition by varying the amount of Ferrous Chloride in the range of 22 to 52 g / l while maintaining it were shown in (Examples 36 to 41).
상기한 본 발명의 전해액을 이용하여 소망하는 조성의 Fe-Ni 합금을 제조하기위한 장치는 특별히 한정되지 않지만, <표1∼6>에 나타낸 (실시예1∼41)의Ni 합금 박판을 제조하기 위해 <도 1>의 배치형 전기도금(성형)장치를 제작하여 이용하였다. <도 1>에서, 전해조(9)에 본 연구에서 발명한 전해액(3)을 넣고 간격거리가 10 mm인 음극(1)과 양극(2) 사이를 전해액이 0.1∼2.0m/sec의 유속으로 흘러가도록 순환펌프(5)를 작동하면서 전주도금(성형)을 실시하였다. 두께 20μm의 Fe-Ni합금이 음극에 전착하면 전류공급장치(4)를 멈춘 후, 음극표면으로부터 도금(성형)재를 분리하여 박판을 획득했다. 이 장치에서 양극재는 유속에 따라 경사각도(10)를 달리한다는 특징을 갖고 있다.Although the apparatus for manufacturing the Fe-Ni alloy of a desired composition using the above-mentioned electrolyte solution of this invention is not specifically limited, To manufacture the Ni alloy thin plate of (Examples 1-41) shown to Tables 1-6. In order to manufacture and use the batch type electroplating (molding) apparatus of <Figure 1>. In FIG. 1, the electrolytic solution 3 invented in the present study was placed in the electrolytic cell 9, and the electrolyte solution flowed between the negative electrode 1 and the positive electrode 2 having a distance of 10 mm at a flow rate of 0.1 to 2.0 m / sec. The electroplating (molding) was performed while operating the circulation pump 5 to flow. When the 20-μm-thick Fe-Ni alloy was electrodeposited on the cathode, the current supply device 4 was stopped, and then a plating (molding) material was separated from the cathode surface to obtain a thin plate. In this device, the cathode material is characterized by varying the inclination angle 10 according to the flow rate.
상기한 방법에 의해 제조된 Fe-Ni 합금은, <표1∼6>에 나타낸 전해액의 종류에 관계없이, 합금조성에 따라서만 1∼9μm/m·K 범위의 열팽창계수값을 나타냈다. <표7>은 열팽창측정장치를 이용하여 얻은 열팽창계수의 값을 몇 가지 실시예에 대하여 나타낸 것이다. 상용인바합금이 같은 온도범위에서 1.2∼1.5μm/m·K의 열팽창계수를 갖는 것과 비교하여 본 발명에 따른 인바합금 박판은 우수한 저열팽창 특성을 나타낸다고 할 수 있다.The Fe-Ni alloy produced by the above-described method showed a coefficient of thermal expansion in the range of 1 to 9 µm / m · K only depending on the alloy composition, regardless of the type of electrolyte solution shown in Tables 1 to 6. Table 7 shows the values of the coefficients of thermal expansion obtained using the thermal expansion measuring apparatus for some examples. Compared with the commercially available bar alloy having a thermal expansion coefficient of 1.2 to 1.5 μm / m · K in the same temperature range, it can be said that the invar alloy sheet according to the present invention exhibits excellent low thermal expansion characteristics.
<표7> 본 발명에서 제조한 Fe-Ni 합금의 열팽차계수 (50∼100℃ 범위)Table 7 Thermal Fluctuation Coefficient of Fe-Ni Alloy Prepared in the Present Invention (50 ~ 100 ° C)
본 발명에 의한 Fe-Ni 합금의 또 다른 특징은 그것을 구성하는 결정립(grain)들이 5∼15 nm인 나노결정질 구조란 점이다. X-ray 회절을 이용하여 결정립의 크기분포를 합금조성에 따라 계산한 결과, 인바합금 조성에서 결정립의 크기가 5∼7 nm 정도로 가장 작게 분포하는 것으로 나타났다. 이렇게 나노결정구조를 갖는 경우, 항복강도는 약 2,000 MPa로 기존방식에 의한 인바합금의 항복강도 260∼500 MPa보다 훨씬 크기 때문에 본 발명에 의한 Fe-Ni 합금 박판은 고강도를 요구하는 새로운 용도에의 적용이 가능하다.Another feature of the Fe-Ni alloy according to the present invention is that it is a nanocrystalline structure having 5 to 15 nm of grains constituting it. As a result of calculating the size distribution of the grains according to the alloy composition using X-ray diffraction, the grain size of the invar alloy composition was found to be the smallest in the range of 5-7 nm. In the case of the nanocrystalline structure, the yield strength is about 2,000 MPa, which is much larger than the yield strength of the Invar alloy according to the conventional method, 260 to 500 MPa. Application is possible.
저열팽창특성을 갖는 Fe-Ni합금을 단일공정인 전주성형방법으로 제작하여 제조단가를 크게 저하시킬 수 있으며, 특히 나노결정질 구조를 갖게 함으로써 기계적 성질이 탁월하기 때문에 산업적 이용의 범위를 새롭게 창출할 수 있다.The Fe-Ni alloy with low thermal expansion properties can be manufactured by a single-step electroforming method, which greatly reduces the manufacturing cost. In particular, by having a nanocrystalline structure, the mechanical properties are excellent, thereby creating a new range of industrial applications. have.
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KR100931739B1 (en) * | 2007-10-19 | 2009-12-14 | 성낙훈 | Invar alloy and its manufacturing method |
KR101420755B1 (en) * | 2013-12-02 | 2014-07-17 | 주식회사 나노인바 | Iron-nickel-ternary ternary alloy having low thermal expansion characteristics and method for manufacturing the same |
KR20170001373U (en) | 2015-10-07 | 2017-04-17 | 주식회사 에프에스코리아 | Compact container having flat brush |
KR20200065462A (en) * | 2018-11-30 | 2020-06-09 | (주) 영진아스텍 | Method of manufacturing a fine metal mask for microdisplay based on high resolution and low thermal expansion OLED through heterogeneous multilayer electro-forming and heat treatment |
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US7387578B2 (en) | 2004-12-17 | 2008-06-17 | Integran Technologies Inc. | Strong, lightweight article containing a fine-grained metallic layer |
US7320832B2 (en) | 2004-12-17 | 2008-01-22 | Integran Technologies Inc. | Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate |
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KR100931739B1 (en) * | 2007-10-19 | 2009-12-14 | 성낙훈 | Invar alloy and its manufacturing method |
KR101420755B1 (en) * | 2013-12-02 | 2014-07-17 | 주식회사 나노인바 | Iron-nickel-ternary ternary alloy having low thermal expansion characteristics and method for manufacturing the same |
KR20170001373U (en) | 2015-10-07 | 2017-04-17 | 주식회사 에프에스코리아 | Compact container having flat brush |
KR20200065462A (en) * | 2018-11-30 | 2020-06-09 | (주) 영진아스텍 | Method of manufacturing a fine metal mask for microdisplay based on high resolution and low thermal expansion OLED through heterogeneous multilayer electro-forming and heat treatment |
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