KR102289458B1 - Powder type hydrogen detecting sensor - Google Patents
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- KR102289458B1 KR102289458B1 KR1020200177094A KR20200177094A KR102289458B1 KR 102289458 B1 KR102289458 B1 KR 102289458B1 KR 1020200177094 A KR1020200177094 A KR 1020200177094A KR 20200177094 A KR20200177094 A KR 20200177094A KR 102289458 B1 KR102289458 B1 KR 102289458B1
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- hydrogen
- pigment
- coating layer
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 103
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 103
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 61
- 239000000843 powder Substances 0.000 title description 2
- 238000002845 discoloration Methods 0.000 claims abstract description 43
- 239000011247 coating layer Substances 0.000 claims abstract description 25
- 239000000049 pigment Substances 0.000 claims description 64
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910002367 SrTiO Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 abstract description 52
- 238000001514 detection method Methods 0.000 abstract description 23
- 229920000642 polymer Polymers 0.000 abstract description 17
- 239000003973 paint Substances 0.000 abstract 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 16
- 229910003445 palladium oxide Inorganic materials 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 238000010306 acid treatment Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- -1 platinum group metal oxide Chemical class 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 6
- 230000002427 irreversible effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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Abstract
Description
본 발명은 수분 및 환경 오염을 방지하기 위해 양친성 폴리머 코팅층이 형성된 분말형 수소 감지 센서에 관한 것이다. The present invention relates to a powder-type hydrogen detection sensor in which an amphiphilic polymer coating layer is formed to prevent moisture and environmental contamination.
수소의 특성은 공기 중에서 수소 가스의 농도가 4 ~ 75% 혼합된 상태에서 20μJ 이상의 스파크나 표면온도가 135 ℃ 이상인 물체를 만나면 발화되어 폭발하는 것으로 알려졌다.The characteristic of hydrogen is known to ignite and explode when it encounters a spark of 20 μJ or more or an object with a surface temperature of 135 ° C or more when the concentration of hydrogen gas in the air is 4 to 75% mixed.
무취 무색인 수소의 기존 누출 검사 방식은 전기 화학식, 전기 저항식 및 열전도성 등 원리를 이용하여 수소 가스를 검출하는 장비들을 이용하고 있지만, 대부분 크기가 크고, 제한적이며 과도한 전력 소모를 요구할 뿐만 아니라 검출동작 자체가 폭발 가능성이 있는 환경하에서 이루어지고 있다.Existing leak testing methods for odorless and colorless hydrogen use devices that detect hydrogen gas using principles such as electrochemical, electrical resistance and thermal conductivity, but most are large in size, limited, and require excessive power consumption as well as detection. The operation itself is being performed under a potentially explosive environment.
또한, 기존의 가스 누출 센서들은 소량의 누출 발생시 감지는 가능하나 복잡한 배관 설비 중 정확하게 어디에서 어떤 원인에 의해 누출이 일어나는지 정확한 위치 및 원인을 파악하기 어려운 경우가 많아 신속한 감지 및 대응이 이루어지지 못하고 있다.In addition, although the existing gas leak sensors can detect a small amount of leak, it is often difficult to determine the exact location and cause of the leak in the complex piping facility, where and for what reason, so it is not possible to detect and respond promptly. .
수소 센서가 실용적으로 보급되고 이용되려면, 수소에 대한 고감도 검지 성능을 가지고 수소 이외의 가스, 수증기, 온도 등에 영향을 받지 않아야 하며, 장수성, 높은 정확성, 대량생산, 작은 크기, 낮은 소모 전력, 저렴한 가격 등이 요구된다.In order for a hydrogen sensor to be practically distributed and used, it must have high-sensitivity detection performance for hydrogen and not be affected by gases other than hydrogen, water vapor, temperature, etc., long life, high accuracy, mass production, small size, low power consumption, low cost price is required.
전기 화학식 센서는 외부 환경에 매우 민감하여 수명이 매우 낮고, 열 전도식 센서는 낮은 비용과 넓은 측정 범위를 지니고 있다는 장점이 있지만 저농도의 수소를 측정하는데 어려움이 있고 선택성과 안정성이 떨어진다. 또한 금속 저항성을 이용한 센서는 선택성이 좋고 반응성이 매우 좋아 반응속도가 빠른 장점이 있으나 높은 농도의 수소 기체를 측정하는데 어려움이 존재한다.The electrochemical sensor is very sensitive to the external environment and has a very short lifespan, and the thermal conductivity sensor has the advantages of low cost and wide measurement range, but it is difficult to measure low concentration of hydrogen and has poor selectivity and stability. In addition, the sensor using metal resistance has the advantage of fast reaction speed due to good selectivity and very good reactivity, but there is difficulty in measuring high concentration of hydrogen gas.
이 외에도 여러 수소 센서 물질들이 있으나 모든 조건을 만족하는 센서 물질이 없어 아직까지 연구가 계속 진행 중이다. 수소와 반응하여 변색이 되는 금속을 이용한 수소 센서는 빠른 반응속도와 우수한 선택성을 보이고 수소 농도에 의존하지 않으며 전기식 센서에 비해 오작동이 낮고 외부 환경에 대해 제약이 거의 없어 안정적이다.In addition to this, there are several hydrogen sensor materials, but there is no sensor material that satisfies all conditions, so research is still ongoing. A hydrogen sensor using a metal that changes color by reacting with hydrogen shows a fast reaction speed and excellent selectivity, does not depend on the hydrogen concentration, has a lower malfunction compared to an electric sensor, and is stable because it has almost no restrictions on the external environment.
기존의 화학적 수소 감지 센서는 실리콘 기반으로 경화 시간이 12 ~24시간으로 오래 걸리며 가격이 비싸고 물질의 특성상 수소 투과 정도가 상대적으로 느려 수소 누출 시 색 변환 속도가 느리다.Existing chemical hydrogen detection sensors are silicone-based, which take a long time to cure (12 to 24 hours), are expensive, and have a relatively slow hydrogen permeation rate due to the nature of the material, resulting in slow color conversion in case of hydrogen leakage.
본 발명의 과제는 공기 중의 수분에 의한 환원에 취약한 수소 변색 안료를 보호할 수 있도록 코팅층이 형성되고, 수소 누출 감지를 수십 초 내로 발견할 수 있는 분말형 수소 감지 센서를 제공하는 것이다. An object of the present invention is to provide a powder-type hydrogen detection sensor in which a coating layer is formed to protect a hydrogen-colored pigment, which is vulnerable to reduction by moisture in the air, and can detect hydrogen leakage within several tens of seconds.
상기한 과제를 달성하기 위해 본 발명은,In order to achieve the above object, the present invention,
전이금속 산화물 입자 표면에 부분적으로 부착된 백금족 금속 산화물을 포함하는 수소 변색 안료 코어와,A hydrogen-chromic pigment core comprising a platinum group metal oxide partially attached to the surface of the transition metal oxide particle;
상기 코어를 감싸고, 하기 화학식 1로 표시되는 반복단위를 포함하는 고분자 화합물을 포함하는 코팅층을 포함하는 분말형 수소 감지 센서를 제공한다:It provides a powder-type hydrogen detection sensor including a coating layer surrounding the core and comprising a polymer compound including a repeating unit represented by the following Chemical Formula 1:
[화학식 1][Formula 1]
(상기 화학식 1에서,(In
R1은 C6 내지 C18의 직쇄 또는 측쇄 알킬기이고,R 1 is a C 6 to C 18 linear or branched alkyl group,
m은 8 내지 24의 정수이다).m is an integer from 8 to 24).
본 발명에 따른 수소 감지 센서는 수소 변색 안료를 외부 오염으로부터 보호하며 탁월한 통기성으로 수소 누출 감지를 수십 초안에 감지할 수 있다. The hydrogen detection sensor according to the present invention protects the hydrogen discoloration pigment from external contamination and can detect hydrogen leakage in tens of seconds with excellent air permeability.
도 1은 실시예 1에서 제조된 PdO/TiO2 수소 변색 안료의 수소 접촉에 따른 비가역적 색채 변화를 나타낸 모식도이다.
도 2는 본 발명의 일 실시예에서 폴리(말레익 안하이드라이드-알트-1-옥타데센)으로 PdO/TiO2 수소 변색 안료를 코팅하여 제조된 분말형 수소 센서의 수소 접촉에 따른 비가역적 색채 변화를 나타낸 모식도이다.
도 3은 본 발명의 일 실시예에 따른 분말형 수소 변색 안료의 산 처리 시 음이온(NO3 -) 흡착 위치를 나타낸 모식도이다.
도 4는 PdO/TiO2 수소 변색 안료와 폴리(말레익 안하이드라이드-알트-1-옥타데센) 코팅층이 형성된 PdO/TiO2 수소 변색 안료를 물에 분산시켜 분산도를 관찰한 사진이다.
도 5는 본 발명의 일 실시예에서 수소 변색 안료와, 코팅층이 형성된 수소 변색 안료의 IR 스펙트럼을 도시한 도면이다.
도 6은 본 발명의 일 실시예에서 코팅층이 형성된 수소 변색 안료와, 산 처리된 수소 변색 안료의 IR 스펙트럼을 도시한 도면이다.
도 7은 실시예 1에서 제조한 수소 변색 안료, 이산화티타늄 및 폴리(말레익 안하이드라이드-알트-1-옥타데센)의 산(HNO3) 처리 전과 후 IR 스펙트럼 도시한 도면이다.
도 8은 폴리머 코팅층이 형성된 수소 변색 안료를 산(HNO3) 처리를 했을 때 코팅층인 폴리(말레익 안하이드라이드-알트-1-옥타데센)(Poly(maleic anhydride-alt-1-octadecene, PMAO)의 산 처리 전 후 IR 스펙트럼을 도시한 도면이다.
도 9는 실험예 2에서 수소 감지 센서의 수소 감지능을 확인하기 위해 사용한 실험 장비를 나타낸 모식도이다.
도 10은 본 발명의 일 실시예에서 코팅층이 형성된 수소 변색 안료와, 산 처리된 수소 변색 안료의 수소 가스 유량에 따른 색채 변화 값을 나타낸 그래프이다.1 is a schematic diagram showing the irreversible color change according to hydrogen contact of the PdO/TiO 2 hydrogen discoloration pigment prepared in Example 1;
Figure 2 is an embodiment of the present invention poly(maleic anhydride-alt-1-octadecene) PdO / TiO 2 Irreversible color according to hydrogen contact of a powdered hydrogen sensor prepared by coating a hydrogen discoloration pigment It is a schematic diagram showing the change.
3 is a schematic diagram showing an anion (NO 3 − ) adsorption position during acid treatment of a powder-type hydrogen-colored pigment according to an embodiment of the present invention.
4 is a PdO/TiO 2 hydrogen discoloration pigment and a poly(maleic anhydride-alt-1-octadecene) coating layer formed by dispersing the PdO/TiO 2 hydrogen discoloration pigment in water to observe the degree of dispersion.
FIG. 5 is a view showing an IR spectrum of a hydrogen-chromic pigment and a hydrogen-chromic pigment having a coating layer formed thereon in an embodiment of the present invention.
6 is a view showing an IR spectrum of a hydrogen-colored pigment with a coating layer formed thereon and an acid-treated hydrogen-colored pigment in an embodiment of the present invention.
7 is a view showing the IR spectrum before and after acid (HNO 3 ) treatment of the hydrogen-chromic pigment, titanium dioxide, and poly(maleic anhydride-alt-1-octadecene) prepared in Example 1;
8 is a poly (maleic anhydride-alt-1-octadecene) (Poly (maleic anhydride-alt-1-octadecene, PMAO) coating layer when the polymer coating layer is formed with acid (HNO 3 ) treatment ) is a diagram showing the IR spectrum before and after acid treatment.
9 is a schematic diagram showing the experimental equipment used to confirm the hydrogen detection capability of the hydrogen detection sensor in Experimental Example 2;
10 is a graph showing the color change values according to the hydrogen gas flow rate of the hydrogen color-changing pigment having a coating layer formed thereon and the acid-treated hydrogen color-changing pigment in an embodiment of the present invention.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명의 분말형 수소센서는 전이금속 산화물 입자 표면에 부분적으로 부착된 백금족 금속 산화물을 포함하는 수소 변색 안료 코어와,The powdery hydrogen sensor of the present invention comprises a hydrogen discoloration pigment core comprising a platinum group metal oxide partially attached to the surface of a transition metal oxide particle;
상기 코어를 감싸고, 하기 화학식 1로 표시되는 반복단위를 포함하는 고분자 화합물을 포함하는 코팅층을 포함한다:It surrounds the core, and includes a coating layer comprising a polymer compound including a repeating unit represented by the following formula (1):
[화학식 1][Formula 1]
(상기 화학식 1에서, (In
R1은 C6 내지 C18의 직쇄 또는 측쇄 알킬기이고,R 1 is a C 6 to C 18 linear or branched alkyl group,
m은 8 내지 24의 정수이다).m is an integer from 8 to 24).
상기 수소 변색 안료는 수소 가스에 노출되었을 때 수소 분자와의 반응에 의해 환원되어 화학적으로 비가역적인 변색이 일어나는 물질이면 제한 없이 사용할 수 있다. 구체적으로 수소 변색 안료는 전이금속 산화물 입자 표면에 부분적으로 부착된 백금족 금속 산화물을 포함하는 것을 사용할 수 있다.The hydrogen discoloration pigment may be used without limitation as long as it is a material that is chemically irreversibly discolored by being reduced by a reaction with hydrogen molecules when exposed to hydrogen gas. Specifically, the hydrogen discoloration pigment may include a platinum group metal oxide partially attached to the surface of the transition metal oxide particle.
이때 상기 전이금속 산화물은 SnO2, TiO2, ZnO, VO2, In2O3, NiO, MoO3, SrTiO3, Fe2O3, WO3 및 CuO로 이루어진 군으로부터 선택되는 단일물 또는 2종 이상의 금속 산화물이 가능하다.At this time, the transition metal oxide is SnO 2 , TiO 2 , ZnO, VO 2 , In 2 O 3 , NiO, MoO 3 , SrTiO 3 , Fe 2 O 3 , WO 3 A single material or two or more selected from the group consisting of CuO Metal oxides are possible.
상기 백금족 금속 산화물은 전이금속 산화물 입자를 서포트로 하여 입자 표면에 부분적으로 부착된다. 구체적으로 상기 백금족 금속 산화물은 팔라듐(palladium), 이리듐(iridium), 루테늄(ruthenium), 백금(platinum) 또는 로듐(rhodium)의 산화물이 가능하다.The platinum group metal oxide is partially attached to the particle surface using the transition metal oxide particle as a support. Specifically, the platinum group metal oxide may be an oxide of palladium, iridium, ruthenium, platinum, or rhodium.
도 1은 실시예 1에서 제조된 PdO/TiO2 수소 변색 안료의 수소 접촉에 따른 비가역적 색채 변화를 나타낸 모식도이다.1 is a schematic diagram showing the irreversible color change according to hydrogen contact of the PdO/TiO 2 hydrogen discoloration pigment prepared in Example 1;
도 1을 참조하면, 전이금속 산화물인 TiO2 입자 표면에 부분적으로 부착된 백금족 금속 산화물 중 하나인 PdO는 수소와의 접촉에 의해 환원되면서 베이지색으로부터 검정색으로 비가역적 색채 변화가 일어난다. Referring to FIG. 1 , PdO, one of the platinum group metal oxides partially attached to the surface of TiO 2 particles, which is a transition metal oxide, is reduced by contact with hydrogen and an irreversible color change occurs from beige to black.
상기 화학식 1로 표시되는 반복단위를 포함하는 고분자 화합물은 양친성 고분자로, 소수성 잔기가 외부로 노출되도록 수소 변색 안료 코어를 코팅함으로써 공기 중의 수분에 의한 환원으로부터 수소 변색 안료를 보호할 수 있다. The polymer compound including the repeating unit represented by Formula 1 is an amphiphilic polymer, and by coating the hydrogen discoloration pigment core so that the hydrophobic residue is exposed to the outside, the hydrogen discoloration pigment can be protected from reduction by moisture in the air.
구체적으로, 상기 화학식 1은 하기 화학식 2로 표시되는 반복단위를 포함하는 폴리(말레익 안하이드라이드-알트-1-옥타데센)(Poly(maleic anhydride-alt-1-octadecene, PMAO)일 수 있다:Specifically, Formula 1 may be poly(maleic anhydride-alt-1-octadecene, PMAO) including a repeating unit represented by Formula 2 below. :
[화학식 2][Formula 2]
본 발명의 일 실시예에 따른 상기 폴리(말레익 안하이드라이드-알트-1-옥타데센)은 수평균분자량(Mn) 30,000 내지 50,000 g/mol일 수 있다. The poly(maleic anhydride-alt-1-octadecene) according to an embodiment of the present invention may have a number average molecular weight (Mn) of 30,000 to 50,000 g/mol.
도 2는 본 발명의 일 실시예에서 폴리(말레익 안하이드라이드-알트-1-옥타데센)으로 PdO/TiO2 수소 변색 안료를 코팅하여 제조된 분말형 수소 센서의 수소 접촉에 따른 비가역적 색채 변화를 나타낸 모식도이다.Figure 2 is an embodiment of the present invention poly(maleic anhydride-alt-1-octadecene) PdO / TiO 2 Irreversible color according to hydrogen contact of a powdered hydrogen sensor prepared by coating a hydrogen discoloration pigment It is a schematic diagram showing the change.
공기 중 수분과 같은 외부 오염으로부터 수소 변색 안료를 보호하기 위해 양친성 폴리머인 폴리(말레익 안하이드라이드-알트-1-옥타데센)으로 코팅 또는 캡슐화함에 따라 폴리(말레익 안하이드라이드-알트-1-옥타데센)의 소수성기가 외부로 노출되어 수소 변색 안료가 소수성을 갖게 되며, 수소 접촉에 따라 비가역적인 색채 변화가 일어난다. Poly(maleic anhydride-alt-1-octadecene) as coated or encapsulated with the amphiphilic polymer poly(maleic anhydride-alt-1-octadecene) to protect the hydrochromic pigments from external contamination such as moisture in the air. The hydrophobic group of 1-octadecene) is exposed to the outside, so that the hydrogen-colored pigment has hydrophobicity, and irreversible color change occurs according to hydrogen contact.
본 발명의 일 실시예에서 상기 수소 변색 안료는 표면에 NO3-, BO3 3-, PO4 3-, NO2 -, SO3 2-, SO4 2-, 또는 S2O3 2- 이온이 흡착될 수 있다. 이러한 음이온의 흡착은 질산(HNO3), 붕산(H3BO3), 인산(H3PO4), 아질산(HNO2), 아황산(H2SO3), 황산(H2SO4), 싸이오황산(H2S2O3)과 같은 산처리에 의해 이루어질 수 있다. 구체적으로 산 희석액을 사용하여 수소 변색 안료를 담지한다. 이때 산 희석액의 농도는 0.1몰 이상 2몰 이하인 것이 바람직하고, 담지는 1일 내지 10일 동안 수행한다. In one embodiment of the present invention, the hydrogen discoloration pigment is NO 3- , BO 3 3- , PO 4 3- , NO 2 - , SO 3 2- , SO 4 2- , or S 2 O 3 2- ions on the surface. this can be adsorbed. The adsorption of these anions is nitric acid (HNO 3 ), boric acid (H 3 BO 3 ), phosphoric acid (H 3 PO 4 ), nitrous acid (HNO 2 ), sulfurous acid (H 2 SO 3 ), sulfuric acid (H 2 SO 4 ), thi It can be made by acid treatment such as pentasulfuric acid (H 2 S 2 O 3 ). Specifically, the hydrogen discoloration pigment is supported using an acid diluent. At this time, the concentration of the acid diluent is preferably 0.1 mol or more and 2 mol or less, and the loading is performed for 1 to 10 days.
본 발명의 일 실시예에서 상기 수소 변색 안료는 표면에 Cl- 이온이 흡착될 수 있다. 이러한 음이온의 흡착은 염산, 염화나트륨, 염화칼륨 또는 염화칼슘과 같은 염 처리에 의해 이루어질 수 있다. 구체적으로 염 희석액을 사용하여 수소 변색 안료를 담지한다. 이때 염 희석액의 농도는 0.1몰 이상 2몰 이하인 것이 바람직하고, 담지는 1일 내지 10일 동안 수행한다. In one embodiment of the present invention, the hydrogen discoloration pigment has Cl - ions on the surface. can be adsorbed. Adsorption of these anions can be achieved by treatment with a salt such as hydrochloric acid, sodium chloride, potassium chloride or calcium chloride. Specifically, a hydrogen discoloration pigment is supported using a salt diluent. At this time, the concentration of the salt diluent is preferably 0.1 mol or more and 2 mol or less, and the loading is performed for 1 to 10 days.
도 3은 본 발명의 일 실시예에 따른 분말형 수소 변색 안료의 산 처리 시 음이온(NO3 -)에 의한 수소 변색 안료의 흡착 위치를 나타낸 모식도이다. 3 is a schematic diagram showing the adsorption position of the hydrogen-colored pigment by an anion (NO 3 − ) during acid treatment of the powder-type hydrogen-colored pigment according to an embodiment of the present invention.
도 3을 참조하면, NO3 - 또는 Cl- 과 같은 음이온이 백금족 금속 산화물이 수소와 접촉하여 환원되는 반응이 빠르게 활성화되도록 하는 촉매 역할을 함으로써 수소 변색 안료의 수소 감지 능력이 향상될 수 있다. Referring to FIG. 3 , an anion such as NO 3 − or Cl − serves as a catalyst for rapidly activating a reaction in which a platinum group metal oxide is reduced by contact with hydrogen, thereby improving the hydrogen sensing ability of the hydrogen discoloration pigment.
본 발명의 따른 수소 감지 센서는 분말형태로 사용할 수 있도록 수분 및 및 환경에 의한 오염에 약한 수소 변색 안료를 양친성 고분자로 코팅하여 소수성을 갖도록 하였다. The hydrogen detection sensor according to the present invention was made to have hydrophobicity by coating a hydrogen discoloration pigment, which is weak against contamination by moisture and the environment, with an amphiphilic polymer so that it can be used in a powder form.
이와 같이 오염 방지된 분말형 수소 감지 센서는 사용 환경 및 목적에 맞게 다양한 형태로 변형이 가능하여 수소산업에서의 활용가치가 방대할 것으로 기대되고, 화학적 색 변환 수소 검출 방식을 이용해 육안 식별이 가능하고 기존 방식보다 민감도가 높은 센서로 인하여 수소 산업의 안전도를 크게 상승시키는데 기여할 수 있다. 또한, 다양한 응용 기술과 가격적으로 뛰어난 장점을 가지고 있어서 미진한 수소 센서 시장 개척 및 선점이 가능하고 안전한 수소 경제 발전에 동력이 될 것으로 기대된다. As such, the powder-type hydrogen detection sensor that has been prevented from contamination can be modified into various shapes to suit the environment and purpose of use, and is expected to have enormous utility value in the hydrogen industry. Due to the sensor with higher sensitivity than the existing method, it can contribute to greatly increasing the safety level of the hydrogen industry. In addition, it has various application technologies and excellent price advantages, so it is possible to pioneer and preoccupy the inexhaustible hydrogen sensor market, and it is expected to become a driving force for the development of a safe hydrogen economy.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다.Hereinafter, preferred examples are presented to help the understanding of the present invention.
그러나 하기의 실시예는 본 발명을 더욱 쉽게 이해하기 위하여 제공되는 것일 뿐, 실시예에 의해 본 발명의 내용이 한정되는 것은 아니다.However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited by the examples.
실시예 1 : 수소 감지 센서 제조용 코팅 조성물Example 1: Coating composition for manufacturing hydrogen detection sensor
1. PdO/TiO2 수소 변색 안료의 제조1. PdO/TiO 2 Preparation of hydrogen-chromic pigment
여기서 티타늄 디옥사이드(TiO2)를 지지체로 사용하고 산화 팔라듐(PdO)을 이용하여 수소 변색 안료를 제조하였다.Here, titanium dioxide (TiO 2 ) was used as a support and palladium oxide (PdO) was used to prepare a hydrogen discoloration pigment.
티타늄 디옥사이드 10g에 물 100ml를 혼합하여 티타늄 디옥사이드 슬러리 용액을 제조하였다. 그 다음 상기 용액을 70~80 ℃ 가열한 후 2M 수산화나트륨 용액으로 pH 10~11로 만들어주었다. 이후 2M 묽은 염산 용액 50ml에 염화 팔라듐 1g을 혼합하여 염화 팔라듐 수용액을 제조하여 상기 티타늄 디옥사이드 슬러리 용액에 pH 10~11을 유지하면서 천천히 넣어주었다. 이후 추가적으로 1시간 더 70~80℃로 가열한 후 진공 여과 및 건조를 통해 전체 중량 대비 3wt% 산화팔라듐을 함유하는 티타늄 디옥사이드/산화팔라듐 수소 변색 안료를 수득하였다.A titanium dioxide slurry solution was prepared by mixing 10 g of titanium dioxide with 100 ml of water. Then, the solution was heated to 70 ~ 80 ℃ and made to
2. 코팅층 형성 2. Formation of coating layer
폴리머 코팅(Polymer encapsulation) 작업을 위해 수소 변색 안료 입자를 작고 균일하게 만들어 분산이 잘 되게 만들어 줬다. 즉, 클로로포름(chloroform) 용매에 상기 제조한 수소 변색 안료를 넣고 초음파 조사 장비를 이용하여 10~20분간 4kHz 강도로 초음파를 조사하여 수소 변색 안료 입자 분쇄 및 입자 균일도를 증가시켰다. 이후 초음파 조사가 끝나면 건조 작업을 거쳐 수소 변색 입자만 수득하였다.For polymer encapsulation, hydrogen discoloration pigment particles were made small and uniform so that they were well dispersed. That is, the hydrogen discoloration pigment prepared above was put in a chloroform solvent and ultrasonic wave was irradiated with an intensity of 4 kHz for 10 to 20 minutes using an ultrasonic irradiation equipment to pulverize the hydrogen discoloration pigment particles and increase the particle uniformity. After the ultrasonic irradiation was completed, only hydrogen discolored particles were obtained through a drying operation.
초음파 조사 및 건조 작업이 끝난 수소변색입자 5g과 폴리(말레익 안하이드라이드-알트-1-옥타데센)(Poly(maleic anhydride-alt-1-octadecene: 수평균분자량(Mn) 30,000 내지 50,000 g/mol, Sigma-Aldrich, 제품번호: 419117) 25g을 500ml 클로로포름 용매에 넣어 잘 혼합한 후 초음파 조사기를 이용하여 30분간 12kHz 강도로 조사하였다. 이후, 세척을 위해 모액을 제거한 뒤 클로로포름 첨가 및 원심분리기를 이용하여 상층액을 제거하는 방식으로 2~3회 반복 세척을 거치고 하층부 폴리(말레익 안하이드라이드-알트-1-옥타데센)(Poly(maleic anhydride-alt-1-octadecene)가 코팅된 수소 변색 안료를 80℃ 오븐에서 2시간 건조하여 최종 폴리머가 코팅된 수소 변색 안료 수득하였다.5 g of hydrogen discolored particles and poly(maleic anhydride-alt-1-octadecene: number average molecular weight (Mn) 30,000 to 50,000 g/ mol, Sigma-Aldrich, product number: 419117) 25g was put in 500ml chloroform solvent, mixed well, and irradiated at 12kHz intensity for 30 minutes using an ultrasonic wave irradiator After removing the mother liquid for washing, chloroform was added and centrifuged Hydrogen discoloration with poly(maleic anhydride-alt-1-octadecene) coating on the lower layer after repeated washing 2-3 times The pigment was dried in an oven at 80° C. for 2 hours to obtain a final polymer-coated hydrogen discoloration pigment.
도 4는 상기에서 제조된 폴리(말레익 안하이드라이드-알트-1-옥타데센) 코팅층이 형성된 PdO/TiO2 수소 변색 안료((a))와 PdO/TiO2 수소 변색 안료((b))를 물에 분산시켜 분산도를 관찰한 사진이다. 4 is a poly(maleic anhydride-alt-1-octadecene) coating layer prepared above PdO/TiO 2 hydrogen discoloration pigment ((a)) and PdO/TiO 2 hydrogen discoloration pigment ((b)) This is a picture of the dispersion degree observed by dispersing it in water.
코팅층 형성하기 전 수소 변색 안료는 물에 잘 분산되는 반면, 코팅층 형성된 수소 변색 안료의 경우 코팅층의 외각이 소수성을 갖도록 형성되어 소수성을 띄어 물에 분산되지 않고 물 표면에 뜨는 것을 확인할 수 있었다. Before the formation of the coating layer, the hydrogen color-changing pigment was well dispersed in water, whereas in the case of the hydrogen color-changing pigment formed with the coating layer, the outer shell of the coating layer was formed to have hydrophobicity.
실시예 2: 폴리머 코팅층이 형성된 수소 변색 안료의 약산성 처리 Example 2: Weak acid treatment of hydrogen discoloration pigment with polymer coating layer formed
수소가 누출되었을 때 폴리머 캡슐화 된 수소 변색 안료(PdO@TiO2-PMAO)의 변색 속도 향상을 위해 산 처리를 진행하였다. 제조 방법은 1M의 질산 용액을 이용하여 pH 4.5의 증류수를 준비하고 폴리머 캡슐화 된 수소 변색 안료(PdO@TiO2-PMAO) 0.05g을 pH 4.5의 증류수 10ml에 넣어 7일 정도 보관하여 산 처리를 진행하였다. 이후 증류수를 이용하여 1~2회 세척을 진행하고 80℃ 4~6시간 건조 후 산 처리가 완료된 수소 변색 안료를 수득하였다.When hydrogen leaked, acid treatment was performed to improve the discoloration rate of the polymer-encapsulated hydrogen discoloration pigment (PdO@TiO 2 -PMAO). The manufacturing method is to prepare distilled water of pH 4.5 using 1M nitric acid solution , put 0.05 g of polymer-encapsulated hydrogen discoloration pigment (PdO@TiO 2 -PMAO) in 10 ml of distilled water of pH 4.5, and store for 7 days to proceed with acid treatment did. Thereafter, washing was performed 1 to 2 times using distilled water, and after drying at 80° C. for 4 to 6 hours, acid treatment was completed to obtain a hydrogen discoloration pigment.
실시예 3: 폴리머 코팅층이 형성된 수소 변색 안료의 염 처리 Example 3: Salt treatment of hydrochromic pigment with polymer coating layer formed
0.469M의 NaCl 용액 10ml에 폴리머 캡슐화 된 수소 변색 안료(PdO@TiO2-PMAO) 0.05g을 넣어 7일정도 보관하여 염 처리를 진행하였다. 이후 증류수를 이용하여 1~2회 세척을 진행하고 80℃ 4~6시간 건조 후 염 처리가 완료된 수소 변색 안료를 수득하였다.In 10 ml of 0.469M NaCl solution, 0.05 g of polymer-encapsulated hydrogen discoloration pigment (PdO@TiO 2 -PMAO) was added and stored for 7 days to proceed with salt treatment. Thereafter, washing was carried out 1-2 times using distilled water, and after drying at 80° C. for 4 to 6 hours, the salt treatment was completed to obtain a hydrogen discoloration pigment.
실험예 1: IR 스펙트럼Experimental Example 1: IR spectrum
상기 실시예 1 내지 3에서 제조된 수소 변색 안료와, 코팅층이 형성된 수소 변색 안료를 대상으로 IR 분광분석을 실시하였다. 스펙트럼의 측정 및 분석은 Thermo Fisher Scientific사의 Nicolet 5700 IR 분광기를 이용하여 수행하였으며, 그 결과를 도 5 및 도 6에 나타내었다. IR spectroscopy was performed on the hydrogen-colored pigments prepared in Examples 1 to 3 and the hydrogen-colored pigments having a coating layer formed thereon. Spectra were measured and analyzed using a Nicolet 5700 IR spectrometer from Thermo Fisher Scientific, and the results are shown in FIGS. 5 and 6 .
도 5의 IR 스펙트럼에서 코팅층이 형성된 수소 변색 안료는 2884 cm-1 근처에서 C-H 스트레칭 피크, 1720 cm-1 에서 카복실기 특유 피크인 C=O 스트레칭 피크가 나타나는 것을 확인하였다. FIG hydrogen discoloration pigment coating layer is formed in the IR spectrum of 5 was confirmed that the CH stretching peak, a carboxyl group-specific peak of C = O stretching peak at 1720 cm -1 in the vicinity of 2884 cm -1 appears.
이와 같은 분석을 통해서 폴리(말레익 안하이드라이드-알트-1-옥타데센)의 분자구조에서 나타내는 작용기들의 특성 피크가 제대로 나타나는지 확인할 수 있었으며 이를 통해 수소 변색 안료에 폴리(말레익 안하이드라이드-알트-1-옥타데센)의 코팅층이 잘 형성되었음을 짐작할 수 있다. Through this analysis, it was confirmed whether the characteristic peaks of functional groups represented in the molecular structure of poly(maleic anhydride-alt-1-octadecene) appeared properly. It can be inferred that the coating layer of -1-octadecene) was well formed.
도 6은 본 발명의 일 실시예에서 코팅층이 형성된 수소 변색 안료와, 산 처리된 수소 변색 안료의 IR 스펙트럼을 도시한 도면이다.6 is a view showing an IR spectrum of a hydrogen-colored pigment with a coating layer formed thereon and an acid-treated hydrogen-colored pigment in an embodiment of the present invention.
도 6을 참조하면, 실시예 2의 산처리된 수소 변색 안료의 경우 산(HNO3)처리 후 1540 cm-1 와 1575 cm-1 질산염(nitrate) 진동(vibration) 피크가 나타나는 것을 확인할 수 있었다. Referring to FIG. 6 , in the case of the acid-treated hydrogen discoloration pigment of Example 2, after acid (HNO 3 ) treatment, 1540 cm −1 and 1575 cm −1 nitrate vibration peaks appeared.
추가적으로 질산염에 의한 코팅층 양친성 고분자의 흡착 위치를 확인하기 위해 상기 실시예 1에서 제조한 수소 변색 안료와 이산화 티타늄, 폴리(말레익 안하이드라이드-알트-1-옥타데센)을 산 처리 전후 대상으로 동일한 모델의 분광기를 이용하여 IR분석을 수행하였으며, 그 결과를 도 7과 도 8에 나타내었다.In addition, in order to confirm the adsorption position of the amphiphilic polymer of the coating layer by nitrate, the hydrogen discoloration pigment prepared in Example 1, titanium dioxide, and poly(maleic anhydride-alt-1-octadecene) were subjected to acid treatment before and after acid treatment. IR analysis was performed using the spectrometer of the same model, and the results are shown in FIGS. 7 and 8 .
도 7을 참조하면, 폴리머 코팅을 하지 않은 이산화 티타늄과 수소 변색 안료의 산 처리 전후 IR 스펙트럼을 봤을 때, 산(HNO3)처리 후 수소 변색 안료에서 1419.9 cm-1 N-O 스트레칭 피크가 나타나는 것을 확인하였다.Referring to FIG. 7 , when looking at the IR spectrum before and after acid treatment of titanium dioxide and hydrogen-chromic pigment not coated with polymer , 1419.9 cm -1 NO stretching peak was observed in the hydrogen-colored pigment after acid (HNO 3 ) treatment. .
도 8을 참조하면, 코팅층을 형성하는 양친성 고분자인 폴리(말레익 안하이드라이드-알트-1-옥타데센)을 산 처리 전과 후 IR 스펙트럼의 변화를 확인하였을 때 큰 차이가 나타나지 않았다.Referring to FIG. 8 , when the change in the IR spectrum of poly(maleic anhydride-alt-1-octadecene), which is an amphiphilic polymer forming the coating layer, was observed before and after acid treatment, there was no significant difference.
이와 같은 결과로부터, 산 처리 후 백금족 금속화합물인 PdO와 NO3 - 간 상호작용을 통해 수소 변색 안료 표면에 음이온이 흡착됨을 확인할 수 있었다. From these results, it was confirmed that anions were adsorbed on the surface of the hydrogen discoloration pigment through the interaction between PdO, a platinum group metal compound, and NO 3 − after acid treatment.
실험예 2: 수소 감지능 확인Experimental Example 2: Confirmation of hydrogen detection ability
상기 실시예 1 내지 실시예 2에서 제조된 수소 감지 센서를 도 9와 같은 수소 변색 테스트 장비를 사용하여 1) 수소 가스의 유량(수소가스 농도: 100%, 유량: 500sccm)과 2) 혼합 가스[수소 가스 + 질소 가스]에서 수소 가스의 농도를 달리하여 수소 감지 센서의 성능을 테스트하였다.The hydrogen detection sensor prepared in Examples 1 and 2 was tested using the hydrogen discoloration test equipment as shown in FIG. 9 to 1) the flow rate of hydrogen gas (hydrogen gas concentration: 100%, flow rate: 500 sccm) and 2) mixed gas [ Hydrogen gas + nitrogen gas], the performance of the hydrogen detection sensor was tested by varying the concentration of hydrogen gas.
시간(0~30min)에 따라 수소 감지 센서(Paraffin Type)가 수소 가스에 노출되어 색이 변화하는 것을 확인하고, 그 결과를 도 10에 나타내었다.It was confirmed that the color was changed when the hydrogen detection sensor (Paraffin Type) was exposed to hydrogen gas according to time (0 to 30 min), and the results are shown in FIG. 10 .
수소 가스 농도에 따라 변색 속도 차이를 확인하기 위해 동일 유량에서 수소 가스 농도 / 시간에 따라 실험을 수행(유량 500 SCCM을 기준으로 혼합가스: [H2 gas 10 % + N2 gas 90 %] ~ [H2 gas 90 % ~ N2 gas 10 %]까지 수소 가스 농도를 달리하여 수소감지센서의 색 변환 정도를 측정)하였고, 색 변화 차이를 그래프로 정리하여 그 결과를 도 7에 나타내었다.In order to check the difference in the discoloration rate according to the hydrogen gas concentration, an experiment is performed according to the hydrogen gas concentration / time at the same flow rate (mixed gas based on the
Sigmoidal curve fitting (
[표 1][Table 1]
도 10 및 표 1을 참조하면, 양친성 고분자로 코팅된 수소 변색 안료를 염화나트륨으로 처리하거나 질산으로 처리한 경우, 처리하지 않은 경우 보다 염화나트륨(pH6.3) 처리한 경우 약 20%, 질산(pH4.5)으로 처리한 경우 약 40% 정도 수소감지능력이 더욱 향상되었다. 이로써, 산 혹은 염 처리가 수소감지능력 향상에 미치는 영향을 확인할 수 있었다.Referring to FIG. 10 and Table 1, when the hydrochromic pigment coated with the amphiphilic polymer was treated with sodium chloride or treated with nitric acid, about 20% with sodium chloride (pH6.3), nitric acid (pH4) than when not treated. When treated with .5), the hydrogen detection ability was further improved by about 40%. Accordingly, it was confirmed that the effect of acid or salt treatment on the improvement of hydrogen sensing ability.
Claims (7)
상기 코어를 감싸고, 하기 화학식 2로 표시되는 반복단위를 포함하고, 수평균분자량(Mn)이 30,000 내지 50,000 g/mol의 폴리(말레익 안하이드라이드-알트-1-옥타데센)을 포함하는 코팅층을 포함하고,
상기 수소 변색 안료 코어는 표면에 Cl-, NO3-, BO3 3-, PO4 3-, NO2 -, SO3 2-, SO4 2-, 또는 S2O3 2- 이온이 흡착된 분말형 수소센서:
[화학식 2]
A coating layer surrounding the core, including a repeating unit represented by the following Chemical Formula 2, and containing poly(maleic anhydride-alt-1-octadecene) having a number average molecular weight (Mn) of 30,000 to 50,000 g/mol including,
The hydrogen discoloration pigment core has Cl - , NO 3- , BO 3 3- , PO 4 3- , NO 2 - , SO 3 2- , SO 4 2- , or S 2 O 3 2- ions adsorbed on the surface. Powdered hydrogen sensor:
[Formula 2]
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