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1 29 ISSN Online ISSN D 프린팅용티타늄분말의제조공정및시장동향 황준호 *,**, * 경북대학교첨단정보통신융합산업기술원 ** 경북대학교치과대학첨단치과의료기기개발연구소 Manufacturing Process and Market Trends of Titanium powder for 3D Printing JunHo Hwang*, **, *Institute of Advanced Convergence Technology, Kyungpook National Univ., Daegu, 41566, Korea **Advanced Dental Device Development Institute, Kyungpook National Univ., Daegu, 41940, Korea Corresponding author : hjh@iact.or.kr (Received August 3, 2017 ; Revised August 8, 2017 ; Accepted August 16, 2017) Abstract Titanium, which is called wonder metal has a variety of structural functions. Because of this, Titanium usage is increasing in higher value-added industries. Application technologies related to Titanium are also rapidly developing. Titanium has excellent specific strength and corrosion resistance. It also has a charicteristic of low thermal strain and human-friendly. Due to these characteristics, the Titanium powder is being spotlighted as 3D printing material. Representative methods for producing titanium powders are roughly divided into three processes: gas atomization, hydrogenation-dehydrogenation(hdh), and plasma rotating electrode process(prep). In particular, the water atomizing, which is a typical method for producing metal powder at low cost in general, is not suitable for producing titanium powder for 3D printing. This paper introduces the manufacturing process and market trends of titanium powder for 3D printing. Key Words : Titanium powder, 3D Printing, Gas atomization, Water atomization, Hydrogenation-dehydrogenation (HDH), Plasma rotating electrode process(prep) 1. 서론 현재 3차원형상데이터를기반으로 2차원단면데이터를생성하여소재를적층하는방식으로물체를제작하는 3D프린팅기술은급속도로발전하고있으며, 다양한산업에서수요가증가하고있다. 주로기업용프로토타입제작등에제한적으로사용되었던 3D프린터시장이최근에는우주항공, 의료, 자동차, 기계, 건축, 완구, 패션등다양한산업에서도사용이되고있다. 3D프린팅기술과산업이커짐에따라소재에대한시장형성또한기대되고있다. 특히 3D프린팅소재중최근각광을받고있는티타늄분말 (Ti Powder) 은다양한구조기능성을가지고있으며, 고부가가치산업에서사용되는소재이다. 비강도가우수하고, 내부식 성및저열변형, 인체친화적인특성을가지고있는티타늄은 3D프린터와결합이될만한매우중요한산업적가치를가지고있다. 이글에서는이러한 3D프린팅용티타늄분말에대한시장동향및제조공정특징, 품질특성등에대해서기술하고자한다. 2. 시장동향 3D프린팅용티타늄금속분말은 2014 년연간 47톤의수요량에서최근 2017년에는 3배이상증가한 155톤정도의수요량을예측하고있다. 이에따라시장규모도 297 억원에서 874 억원으로증가하고있다. 특히우수한비강도특성과관련된항공분야가 40% 가량의수요를가지고있다. 또한 2023 년분말생산규모는 582 톤정도, 시장규모는약 2,410 억원의규모로예상하고있다 1). Journal of Welding and Joining, Vol.35 No.4(2017) pp
2 30 황준호 Others Service Bureau Automotive Dental Medical Aerospace Fig. 1 Market size of titanium powder (KRW 100 million) 1) Others Service Bureau Automotive Dental Medical Aerospace 3. 3D 프린팅용티타늄분말제조공정 이러한다양한산업에서수요가증가하고있는티타늄분말을제조하는대표적인방법은가스아토마이징 (Gas Atomizing), 수소화-탈수소화법 (HDH, Hydrogenation- Dehydrogenation method), 플라즈마회전전극분무법 (PREP, Plasma Rotating Electrode Process) 이상 3가지제조공정으로크게나뉜다. 그러나티타늄원소재인 TiO 2 는산소를다량함유하여공업적으로사용이어렵기때문에분말제조전환원을하여제련이가능한상태로변환을해주어야한다. 이러한작업이이루어지기위해선행작업으로 Kroll Process 가공통적으로포함이되며이후위의각기다른방법으로분말을제조하게된다. 그에따른분말제조공정기법의특징들은다음과같다. 3.1 가스아토마이징 Fig. 2 Product titanium powder (ton) 1) 가스아토마이징 (Gas Atomizing) 기법은미세한구멍을통하여유출되는용융티타늄을고압의가스또는액체를이용하여분산시켜분말화하고, 진공챔버내에비산과급냉을시켜입도가 50~350 μm수준인구형의티타늄분말제조가가능하다 2,3). Fig. 3 (a) 와 (b) 는각각대표적인분말제조업체인 LPW( 영국 ) 와 SANDVIK Table 1 Market size of titanium powder in the industrial sector 1) Ti[100million (KRW)/year] Aerospace Medical Dental Automotive Service Bureau Others Total ,250 1,492 1,777 2,022 2,100 2,410 Table 2 Production size of titanium powder in the industrial sector 1) Ti[ton/year] Aerospace Medical Dental Automotive Service Bureau Others Total Journal of Welding and Joining, Vol. 35, No. 4, 2017
3 3D 프린팅용티타늄분말의제조공정및시장동향 31 사 ( 스웨덴 ) 에서제조하는방식으로가스속도로분말의크기를제어하며, 구형의분말을제조하는데효율적이나도가니사용으로인한오염등의문제가발생될수있는단점이있다. 이를보완하기위해 Fig. 3 (c) ALD 사 ( 독일 ) 에서는봉재를이용한 Electrode Induction melting Gas Atomizing 방식을이용하고있으며, Fig. 4 는티타늄봉재를용융시키는과정을나타내고있다. Gas source and pump Fine powder (a) Vacuum induction meter Collection chamber Nozzle (b) 3.2 수소화탈수소화기법수소화탈수소화 (HDH) 기법은티타늄소재의수소흡장성질을이용하여분말을제조하며, 낮은온도에서의수소고용량의특징을이용하므로수소취화작업과이후볼밀링공정을한다 4). 볼밀링공정에서는 50~300 μm크기수준의분말이형성되고진공어닐링열처리를행하여수소를제거한다. 그러나이제조공정은각각의입자들이불규칙적인입자형상과 5000ppm 이상의높은산소농도를보인다. 특히이러한불규칙한입자형상과높은산소농도는적층시적층물의형상정밀도가낮아지며, 적층단면의기공등으로인해기계적인물성저하가우려되기에 3D 프린팅소재로는매우부적합하며, 플라즈마를이용한구상화 (Plasma Spheroidizing) 처리가반드시필요하다. Fig. 5는플라즈마처리전후의분말형상을나타내고있다. 3.3 플라즈마회전전극분무기법 플라즈마회전전극분무 (PREP) 기법은용해된티타늄회전체를이용하여원심력에의해서용융티타늄을제조하는방식이다. 이공정에서는전극회전속도에따라분말크기를제어할수있으며, 100~300 μm크기의구형인유동성이좋은분말을제조할수있다 5). (c) Fig. 3 Manufacturing process of titanium powder (Gas Atomizing) (a) LPW Manufacturing mode, (b) SANDVIK Manufacturing mode, (c) TLS Manufacturing mode <Before plasma treatment> <After plasma treatment> Fig. 5 Powder shape before and after plasma spheroidizing treatment in HDH Plasma gas Electrode Protective sleeve Nozzle Protective gas Plasma arc Fig. 4 Melting process of titanium Fig. 6 Manufacturing process of titanium powder (PREP) (a) LPW Technology Inc (b) AWL- Techn 대한용접 접합학회지제 35 권제 4 호, 2017 년 8 월 335
4 32 황준호 3.4 수분사기법또한일반적으로저렴하게금속분말을제조하는대표적인방식인수분사 (Water Atomizing) 기법으로 3D 프린팅용티타늄분말을제조한다면, 물과불활성가스간의제약조건이필요하며물의압력은 50~300bar, 물의토출량은 50~500l/min, 가스의압력은 10~50bar 정도의제약조건하에서생산을해야한다. 그러나수소화탈수소화 (HDH) 기법과같이형상의불규칙적인문제가예상되며, 티타늄은액적화가잘되지않는특유의특성과산화제어가매우어렵기때문에수분사 (Water Atomizing) 기법으로품질이우수한티타늄분말을제조하는것은매우어려울뿐만아니라적합하지않은제조방법이기도하다 5). Fig. 7은입자형상이불규칙한분말을사용하여적층한 3D 프린팅출력물로적층품질이양호하지못한것을나타내고있다 D 프린팅용티타늄분말의조건 3D프린팅분말소재로사용이되기위해서는입자의형상이구형에가깝고입자크기의공차가적을수록적층시우수한출력물을제조할수있다. 티타늄분말도마찬가지이며최적의적층공정을가지기위한분말의조건은 10~60μm (D50: 45μm ) 크기이며, 구형의입도형상, 고른입자분포형성, Tap density( 밀도분포 ) 65% HDH (LPW Technology Inc) Atomizing (Advanced Powders and Coatings Inc.) PREP (Advanced Powders and Coatings Inc.) Fig. 7 3D printing output made from irregularly shaped powder Fig. 8 Particle shape type according to manufacturing process Table 3 Component analysis of Ti powders manufactured by gas atomizing(c&l Development Corp.) O Cl H N C Si Mg Fe Ti -150 (>90%) Bal. -75 (>90%) Bal. -45 (>90%) Bal. Table 4 Component analysis of Ti powders manufactured by PREP(C&L Development Corp.) O Cl H N C Si Mg Fe Ti -840 (>90%) Bal (>90%) Bal (>90%) Bal. 150 (>90%) Bal. Table 5 Component analysis of Ti powders manufactured by HDH(Sumitomo Titanium Corp.) O Cl H N C Si Mg Fe Mn Ti -150/ Bal Bal. -150/ Bal Bal. 336 Journal of Welding and Joining, Vol. 35, No. 4, 2017
5 3D 프린팅용티타늄분말의제조공정및시장동향 33 이상의조건을가져야한다. SLS/SLM 방식 (PBF) 의 3D프린터는이러한조건을충족해야최적공정이수립되며, 또한 2kW 급이상고출력레이저를이용하는 DED 메탈 3D프린터역시 PBF방식보다넓은 45~150 μm입도분포의분말을사용해도무방하나반드시구형의입자형상을사용해야만우수한품질의적층물을제조할수있다 6). 티타늄분말성분구성은산소, 염소, 수소, 질소, 탄소, 규소, 마그네슘, 철, 티타늄으로구성이되어있으며, 각각의제조공정중주된변동성분은산소와철이주를이룬다. 이중에서도티타늄은산소친화력이강하므로산소의변동에따라티타늄분말의전반적인성분구성이바뀐다. 그러므로공통적인분말제조방법은진공상태혹은불활성분위기에서티타늄분말을제조하며, 동일한원소재의불순물과용해분위기가유사한경우거의동일한순도와특성을나타내는티타늄분말을제조할수있다. 특히티타늄의강도, 연신율등기계적인특성변화는산소함유량에대해크게영향을받는다. 이러한산소함유량의정도가티타늄파우더특성에큰영향을주며, 조절하는방법으로는대기반응을줄임으로써산소의농도를 400ppm 수준이하로관리하는방안이일반적이다 7). 3.6 티타늄분말제조신기술기존의 Kroll process 에서제조되는티타늄스폰지를재용해하여분말을만드는방법은고품질의티타늄분말을제조할수있으나고가의제조비용이발생되는단점이있다. 최근에는제련기술발달에따라원광석에서티타늄분말을제조할수있는신기술들이소개되고있다. Armstrong 법은저온에서연속적으로환원하며제조할수있기에가격경쟁력이있으며, 산소함유량도 500ppm 수준으로관리할수있는특징이있다. 또한티타늄원광석직접환원법인고온염욕제련법 (Molten Calcium Chloride) 은약 1000 에서티타늄스폰지와분말을제조하는방법으로산화물의환원과합금을동시에이룰수있고산소함유량도 100ppm 이하로관리할수있는특징을가지고있다 8). 4. 결론 위와같이티타늄은고가의제조비용및제조공정의 어려움에도불구하고 3D프린팅기술과접목하였을때가장큰반향을일으킬수있는소재이다. 특히우주항공, 국방, 선박, 의료분야등여러산업에적용가능성이높은소재이며 20여년전부터티타늄시장은증가하고있으므로다양한제조업기반의수요처가생길것으로보인다. 국내 3D프린팅기술 (HW, SW) 은세계수준대비 10년이상뒤쳐져있어시장주도권확보가어려운실정이다. 하지만저렴한비용으로티타늄합금소재를제조할수있는기술을개발한다면향후 4차산업혁명의핵심인 3D프린팅기술의소재시장주도권을확보하고선진기술을선도할수있을것으로기대된다. 감사의글 본연구는산업통상자원부의 레이저응용의료기기 / 첨단소재가공산업기반구축 및 표면정밀도 7μm급대형부품직접제작용금속 3D 프린터개발 사업의일환으로수행되었음. References 1. Additive Manufacturing in the Metal Powder Industry, Smartech Market Publishing, (2014) 2. A. J. Heidloff, J. R. Rieken, I. E. Anderson, Advanced gas atomization processing for Ti and Ti alloy powder manufacturing, The Journal of The Minerals, 62 (2010), Andrew J. Heidloff, Joel R. Rieken, Iver E. Anderson and David Byrd, ADVANCEMENTS IN TI ALLOY POWDER PRODUCTION BY CLOSE-COUPLED GAS ATOMIZATION, (2011), X Goso and A Kale, PRODUCTION OF TITANIUM METAL POWDER BY THE HDH PROCESS, Light Metals Conference, (2010), 유지훈, 양상선, 김용진, 임태수, 3D 프린팅용금속분말소재의연구및개발동향, 기계와재료, 28(1) (2016), (in Korean) 6. Jun-Ho Hwang, Seong-Seon Shin, Gu-In Jung, Sung- Wook Kim and Hyun-Deok Kim, A Study on the Characteristics of Laser Deposition Suface and Cross-section for Metal Powder, J. of Welding and Joining, 34(4) (2016), (in Korean) 7. Jai-Sung Lee, R&D Strategy for 3D Printing Metal Powders, J. Korean Powder Metall. Inst., 22(2) (2015) ((in Korean) 8. 박노광, 홍재근, 김정한, 염종택, 타이타늄분말합금의제조와특징, 기계와재료, 21(2) (2009), (in Korean) 대한용접 접합학회지제 35 권제 4 호, 2017 년 8 월 337
내지 28권1호 색상변환.indd
[ 특집 : 3D 프린팅과소재 ] 3D 프린팅용금속분말소재의연구및개발동향 유지훈, 양상선, 김용진, 임태수 재료연구소 3D 프린팅기술은주 / 단조, 압출, 사출, 용접등과같은기존의성형가공공정에비해복잡형상의제조가용이하고, 제조시간및비용을절감할수있을뿐만아니라, 수요자가요구하는맞춤형부품의소량다품종생산이가능하므로기존의제조산업패러다임을바꿀혁신적기술로급격하게부상하고있다.
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