Nghiên cứu phát triển các hệ phổ kế huỳnh quang tia x và ứng dụng trong phân tích thành phần vật liệu ở Việt Nam

Hoi nghi Khoa hoc ky'niem 35 ndm Vien Khoa hoc vd Cong nghe Viet Nam - Hd Noi 10/2010<br /> <br /> <br /> <br /> NGHIEN Ciru PHAT TRIEN CAC HE PHO KE HUYNH QUANG TIA X<br /> VA iTNG DUNG TRONG PHAN TICH THANH PHAN VAT LIEU 6<br /> VIET NAM<br /> <br /> Le Ouang Huy, Nguyen The Quynh va Dao Tran Cao<br /> Vien BChoa hpc Vat lieu<br /> 18 - Hoang Qudc Viet, quan Cau Giay, Ha Ndi<br /> Email: IqhuyfSjims.vast.ac.vn<br /> Tdm tdt:<br /> Bdo cdo trinh bdy mdt sd kit qud nghien ciru che tgo vd phdt trien ung dung<br /> mdy phd ke huynh quang tia X de phdn tich thdnh phdn nguyen td cita vdt lieu tgi<br /> Viet Ngm. Cho den nay, khodng 50 he mdy phd ke huynh quang tia X (PKHQTX)<br /> vdi cdc cdu hinh khdc nhau dd dugc che tgo vd dua vdo su dung. Vdi su edi tien<br /> lien tuc cd ve phdn cdng Idn chuang trinh phdn tich, cdc he mdy cd cdu hinh don<br /> gidn, ggn nhe da dugc cung cdp cho cdc ca sd kinh doanh, che tdc dd trang sire<br /> tgi nhieu tinh thdnh. Cdc thiet bi ndy gdp phdn quan trgng ddm bdo chdt lugng<br /> ciia cdc sdn phdm vdng, bgc tren thi trudng trong nude, mang lgi lgi ich thiet thuc<br /> cho ngudi tieu diing vd cdc dognh nghiep. Ddc biet, he mdy XRF5006-HQ02 cd<br /> ddu thu tia X ldm lanh bdng pin Peltier vd ngudn kich mdu Id den tia X cimg<br /> chucmg trinh phdn tich dinh lugng XRF-FP se Id thiet bi phdn tich hien dgi cd the<br /> ung dung hiru hieu trong cdng nghiep khai thde vd che bien khodng sdn. He mdy<br /> ndy dugc su dung de kiem sodt qui trinh cdng nghe vd chdt lugng sdn phdm, gdp<br /> phdn ndng cao hieu qud sdn xudt ciia cdc doanh nghiep.<br /> <br /> Abstract:<br /> This report presents some results of manufacture and developing application of<br /> the X ray fluorescence spectrometers for analytical elemental constituents of<br /> materials in Vietnam: Up to now, about 50 X-ray fluorescent spectrometers<br /> (XRFS) with different configurotion are fabricated and in use. With continuous<br /> improvements in both hardware and analytical software, the simple and<br /> comfortable XRFS are supplied for jewelry trade gnd producing shops in many<br /> towns. These XRFS have contributed importantly to control the quality of golden<br /> and silver products on the domestic market and that brought useful benefit for<br /> both people and businessman. Especially, the XRFS model XRF5006-HQ02<br /> having a X-ray detector cooled by Peltier battery, an X-ray tube as exciting<br /> source and XRF-FP analytical quantitative software will be a modern analytical<br /> equipment that can be applied effectively fgr minergl exploiting and processing<br /> industry. This machine will be used to control the technological process and the<br /> quality of products, and contributed to improve the efficiency of factories.<br /> <br /> <br /> <br /> 51<br /> Tieu ban: Cong nghe thong tin - Tu dong hod - Cong nghe Vu tru ISBN: 978-604-913-010-6<br /> <br /> <br /> <br /> G I 6 1 THIEU<br /> Phd kl huynh quang tia X dugc sir dung rat rdng rai tren thi gidi dl phan tich dinh tinh<br /> ciing nhu dinh lugng thanh phan nguyen td cua vat lieu ma khdng phu thugc vao lien ket hoa<br /> hpc cua chiing. U'u diem ndi bat ciia phuong phap nay la phan tich nhanh ddng thdi nhieu<br /> nguyen td, khdng pha huy mau va mau cd the d nhieu dang khac nhau: rin, Idng, klii. Nguyen<br /> ly hoat ddng ciia he may la khi nguyen tir ciia mdt nguyen td nao dd cd trong mau dugc kich<br /> thich bdi photon (thudng la tia X hay tia y) hay hat mang dien (nhu dien tir) cd nang lugng<br /> thich hgp thi chiing se phat ra cac tia X cd nang lugng xac dinh, dac trung cho nguyen td do.<br /> Detecto se thu cac tia X nay va bien ddi chiing thanh cac xung dien cd bien dp ti le tuyen tinh<br /> vdi nang lugng cua tia X. Tiep theo, cac xung dien nay se dugc khuech dai, tao dang thich<br /> hgp va bien doi thanh dang tin hieu sd de may tinh thu thap va xir ly, cho ta phd huynh quang<br /> tia X ciia mau vdi true hoanh la nang lugng (hay budc sdng cua tia X), true tung la sd dem cac<br /> tia X cd cac mire nang lugng khac nhau. Xir ly thdng tin ve vi tri dinh ciia cac vach phd cho ta<br /> biet trong mau cd nhirng nguyen td nao (phan tich dinh tinh), xir ly thdng tin ve cudng dp<br /> (dien tich) vach phd cho ta biet ham lugng cac nguyen td dd trong mlu (phan tich dinh<br /> lugng).<br /> <br /> LTnh vuc iing dung ciia PKHQTX rat rdng rai nhu: kiem soat qui trinh cdng nghe san xuit<br /> vat lieu (xi mang, kim loai mau, vat lieu xuc tac, che tac do trang siic, ...), tham dd, khai thac<br /> va che bien khoang san, nghien ciiu khoa hpc, khao cd hpc, y-sinh hpc, ndng nghiep, mdi<br /> trudng, ...<br /> <br /> Hudng nghien ciin ehl tao PKHQTX va phat triln ung dung phuang phap phan tich nay da<br /> dugc tien hanh tir nhieu nam nay va thu dugc nhilu kit qua kha quan. Cho din nay, 4 loai<br /> PKHQTX da dugc che tao va dua vao sir dung, gdm 2 ddng san phim la: PKHQTX sir dung<br /> detecto Si(Li) lam lanh bang nito Idng (hien chi cdn khoang 15 he may dang hoat ddng) va<br /> PKHQTX sir dung detecto Si-PIN lam lanh bing pin nhiet dien (hien cd khoang 35 he may).<br /> Vi ly do kT thuat cung nhu dl phat triln img dung cho nhilu ITnh vuc khac nhau, hien tai<br /> chiing toi chi phat trien loai PKHQTX cd diu thu tia X lam lanh bing pin nhiet dien.<br /> Trong bai bao nay chiing tdi se trinh bay cac dac tinh chung cung nhu kit qua img dung<br /> ciia hai ddng san pham chinh dua tren cac img dung thuc tl hien nay la PKHQTX cd ngudn<br /> kich mau bang ngudn ddng vi phdng xa (iing dung trong ITnh vuc san xuit, kinh doanh dl<br /> trang sire) va PKHQTX cd ngudn kich thich mau bing den phat tia X (iing dung trong nghien<br /> ciiu khoa hpc va cdng nghiep khai thac chi biln khoang san).<br /> <br /> CAu TAO CHUNG CUA THIET BI VA PHAM VI I T N G DUNG<br /> Tia X CO ban chat ludng tinh: vira la sdng (dac trung bing budc sdng), vira la hat (dac trung<br /> bang nang lugng) nen de ghi phd ciia chiing ngudi ta da chi tao ra hai loai phd kl dua tren<br /> ban chat ludng tinh nay, dd la: phd kl huynh quang tia X phan tach cac tia X bing budc sdng<br /> (X-ray Wavelength Dispersive Spectrometer - WDS) va phd kl huynh quang tia X phan tach<br /> cac tia X theo nang lugng (X-ray Energy Dispersive Spectrometer - EDS).<br /> <br /> 52<br />  2010<br /> Hoi nghi Khoa hoc ky niem 35 ndm \ 'ten Khoa lioc vd Cong nghe Viet Nam - Hd Noi 10'2<br /> <br /> <br /> <br /> <br /> Solid state<br /> X-ray detector<br /> <br /> <br /> <br /> X-ray<br /> source Primary<br /> radiation filter<br /> (tube only)<br /> <br /> Pulse<br /> FVocessIng<br /> <br /> <br /> <br /> i<br /> Integrated %<br /> microprocessor ><br /> or PC<br /> ri-L:-iu<br /> /mill\\\\\\\^<br /> <br /> <br /> Hinh 1: Sa dd nguyen ly ciia he phd ke huynh quang tia X kiiu EDS<br /> <br /> Sau day, chiing tdi chi de cap den loai phd ke kilu EDS ma nguyen Iy ciu tao cua nd<br /> dugc bieu dien tren hinh 1, gdm 3 phin chinh dd la:<br /> - Ngudn kich thich mau: la ngudn ddng vi phdng xa hoac den phat tia X cdng suit nhd.<br /> - Bd phan thu tia X ma thdng thudng la cac detecto ban din.<br /> - Cac bd phan dien tir thich hgp ciing phan mem ghi va xir ly phd, tinh toan ham lugng.<br /> A. Loai PKHQTX su- dung nguon dong vi phong xa di kich thich mau<br /> Loai phd ke nay cd cau hinh don gian, gpn, de thao tac va sir dung vi nguon kich thich mau<br /> la ddng vi phdng xa cd kich thude nhd (dudng kinh ngudn < 10mm). Trong qua trinh nghien<br /> ciiu phat trien, chiing tdi da che tao dugc hai loai phd kl kilu nay. He may sir dung detecto<br /> Si(Li) lam lanh bang nita Idng dugc che tao va dua vao sir dung tir nam 1989. Din nay cdn<br /> khoang 15 he dang hoat ddng tai cac doanh nghiep. U'u dilm ciia loai nay la hoan toan dugc<br /> che tao trong nude nen viec bao tri, sira chiia rat chii ddng. Tuy nhien, vi cin phai diing nito<br /> long de lam lanh nen khdng thuan tien va chi phi van hanh khdng nhd (vi thudng 2 tuin cin<br /> phai bd xung nita Idng mdt lan). De khac phuc yeu diem tren va md rdng ban nira dia ban iing<br /> dung, tir cudi nam 2006 chung tdi dua ra model mdi sir dung diu thu tia X chi cin lam lanh<br /> bang pin nhiet dien. Vdi nhirng cai tien thiet ke va chuong trinh phan tich, he may nay cd dp<br /> chinh xac cao hon so vdi loai cd dau thu tia X lam lanh bang nita Idng nhung kich thude rit<br /> nhd gpn va quan trpng hon ca la khdng can sir dung nita Idng. Hinh 2a la he may thude model<br /> dau tien (XRF2500-12N) cd dau thu tia X lam lanh bing pin Peltier va hinh 2b la model mdi<br /> nhat cua loai may nay (XRF2500-12LC). Nhd cac uu dilm vugt trdi so vdi he may phai diing<br /> nito Idng ma trong vdng ba nam qua. chiing tdi da cung cip cho thi trudng dugc 35 he may<br /> loai nay (gan gap hai lan sd may da chi tao dugc trong 15 nam trudc do).<br /> <br /> <br /> <br /> <br /> 53<br /> Tieu ban: Cong nghe thong tin - Tu dong hod - Cong nghe Vii tru ISBN: 978-604-913-010-6<br /> <br /> <br /> <br /> <br /> Hinh 2a: He phd ki thi he mdi cd ddu thu tia X lain Hinh 2b: Model XRF2500-12LC vdi nhieu<br /> lanh bdng pin nhiet dien vd kich mdu bdng ngudn tinh ndng ki thudt dugc edi tien vd sir dung<br /> ddng vi phdng xg, model XRF2500-12N tien lai han XRF2500-12N<br /> <br /> • Dac tinh kT thuat chung ciia loai may nay la:<br /> - Diu thu tia X lam lanh bang pin nhiet dien cd dp phan giai nang lugng cd 200eV.<br /> Kich thich mau phan tich bang ngudn ddng vi phdng xa Am "".<br /> Cd the phan tich dugc cac nguyen td cd Z>22 (tir nguyen td Ti) trd di.<br /> Thdi gian phan tich mau tir 30H-90 giay tuy thude loai mau.<br /> - Kich thude: 35x35x25cm, khdi lugng: 11 kg, tieu thu dien: 60W/220Vac<br /> Sir dung cue ky don gian, tien lgi.<br /> • Ung dung chii yeu hien tai la ITnh -vuc che tac va kinh doanh dd trang sire lam bang vang,<br /> bac. Cac chuong trinh phan tich dinh lugng ngay cang hoan thien hon: ban dau chi xay<br /> dung chuong trinh tinh thanh phan gdm 2 nguyen td la Au va Ag, tiep theo phat trien<br /> them chuang trinh phan tich thanh phan cua vang tay truyen thdng gdm: Au, Ag va Cu; va<br /> hien tai da phat trien chuong trinh phan tich cho hgp kim nhilu thanh phin gdm: Au, Ag,<br /> Ni, Cu, Zn, Sn, Pd va ca Pt de cd the phan tich dugc thanh phan ciia tat ca cac san pham<br /> trang sire. Vdi cac qui trinh phan tich ngay cang hoan thien hon, cac he may nay dat dp<br /> chinh xac:<br /> <br /> - Tir 0,1 ^ 0,5% ddi vdi san pham vang ta (chi gdm: Au va Ag) phu thude vao hinh<br /> dang, dp ddng deu va kich thude ciia mau; tudi vang cang cao thi sai sd cang nhd.<br /> - Tir 0,3 H-1,5% doi vdi san phim vang tay (gdm: Au, Ag, Ni, Cu, Zn, Sn va Pd) hoac<br /> bach kim (Pt, Cu, Ni, Pd, Rh).<br /> - Tir 1^2% ddi vdi cac san pham chi tac tir bac (gdm Ag, Cu, Zn) hay hdi vang (cd thi<br /> gdm: Ag. Ni, Cu, Zn, Sn, Pd).<br /> • Cac tinh. thanh phd da lap dat may phan tich gdm: Ha Ndi, Hai Phdng, Nam Dinh, Thai<br /> Nguyen. Bic Ninh. Hung Yen, Ninh Binh, Thanh Hoa, Nghe An, Bic Can, Ha Giang, Lao<br /> Cai. Lai Chau. Son La, Viet Tri, Quang Ninh. Cac he may nay da gdp phan quan trpng<br /> trong \'iec on dinh chat lugng san pham nir trang trong pham vi toan qudc va mang lai lai<br /> ich thiet thuc cho ngudi tieu dung ciing nhu cac doanh nghiep kinh doanh, chi tac dd<br /> trang sire.<br /> <br /> 54<br />  Hoi nghi Khoa hoc ky niem 35 ndm Vien Khoa hoc vd Cong nghe Viet Nam - Hd Noi 102010<br /> <br /> <br /> <br /> B. Loai PKHQTX dung den tia X dl kich thich mau<br /> Loai PKHQTX diing ngudn ddng vi phdng xa de kich mau tuy cd uu diem la gpn nhe. de<br /> sir^dung va don gian, nhung cac ngudn phong xa ndi chung chi phat ra photon don nang nen<br /> mdi ngudn phdng xa chi thich hgp de phan tieh cho mdt sd nguyen td nhat dinh. Vi the, thdng<br /> thudng de cd the phan tich dugc nhieu nguyen td thi mdi he may nhu vay thudng phai cd tir 2<br /> den 3 ngudn ddng vi khac nhau va thdi gian ban ra ciia cac ngudn nay thudng ngan (\'i du:<br /> ngudn Fe 55 cd thdi gian ban ra la 2,7 nam, ngudn Cd la 1,3 nam) nen hieu qua kinh tl<br /> khong cao. De khac phuc yeu diem tren, den phat tia X dugc thay thi cac ngudn phdng xa<br /> nay. Viec sir dung den tia X cho phep thay ddi ca cudng dp va nang lugng biic xa kich thich<br /> mau bang each thay ddi the va ddng nudi den. Mat khac, den tia X thudng cd cudng dp phat<br /> xa^manh hon cac ngudn phdng xa thdng dung cd 10^-HIO' lin, do dd giam dugc thdi gian do<br /> mau, tang dugc dp nhay ciia may, an toan hon cho ngudi sir dung va khdng gay d nhiem mdi<br /> trudng. He may sir dung den phat tia X cdng suit nhd lam ngudn kich mau va detecto Si(Li)<br /> lam lanh bang nito Idng model EDS-XT99 da dugc nghien cuu ehl tao va dua vao boat ddng<br /> tir nam 2000 nhu chi ra tren hinh 3. Cac thdng sd kT thuat chinh cua he may nay la [ 1, 2]:<br /> <br /> <br /> <br /> <br /> Hmh 3: He mdy PKHQTX cd ngudn kich thich mdu Id den phdt tia X kiiu EDS-XT99<br /> do Vien Khoa hoc Vdt lieu chi tgo ndm 2000.<br /> - Detecto thu tia X loai Si(Li), do day 5mm, dien tich 20mm^ lam lanh bing nito Idng.<br /> - Dp phan giai nang lugng do tai vach 5,9keV dat 180eV.<br /> - Ngudn kich mau la den phat tia X cd anode bing Rh, thi anode cue dai 50kV. cdng<br /> suat 50W lien tuc, dugc dilu khiln kT thuat sd va cd thi sir dung theo 3 kilu: kich<br /> thich bang tia X phat ra true tilp tir den; bing tia X don nang phat ra tir bia thir cip<br /> lam tir kim loai tinh khilt khac nhau nhu: Cu, Ge, Mo, Zr; hoac kit hgp kich mau<br /> bang ca den va ngudn phdng xa Am^'*'.<br /> <br /> <br /> 55<br /> Tieu ban: Cong nghe thong tin - Tir dong hod - Cong nghe I 'u tru ISBN: 978-604-913-010-6<br /> <br /> <br /> <br /> - Gidi han phat hien cue tieu tuong ddi ciia nhieu nguyen td cd mdt vai chuc ppm-<br /> - Dp dn dinh dat cd 0,3%/ 8gid va dp lap lai dat cd 0,5-^1%.<br /> - Cira sd Be day 8|J.m nen cd the phan tich dugc cac nguyen td tir Mg trd di trong bang<br /> tuan hoan (Z>12).<br /> - Mau cd the dugc do trong mdi trudng chan khdng<br /> <br /> • Vdi cac thong so ki thuat tuong ddi tdt, he may dau tien sir dung den tia X lam ngudn kich<br /> mau EDS-XT99 da dugc ung dung de:<br /> - Phan tich thanh phan nguyen td eiia men mau tren dd gdm, sir khao cd [3,4].<br /> - Phan tich thanh phan kim loai cd trong tdc [5,6].<br /> - Phan tich kim loai trong nude thai cdng nghiep [7].<br /> - Phan tieh tap chat trong vat lieu dng nano cac bon [8]<br /> - Phan tich thanh phan va xac dinh chieu day mang mdng Fe-Ni [9]<br /> - Phan tich thanh phan ciia do ddng cd [ 10].<br /> - Phan tich thanh phan cac san pham trong qui trinh chiit tach va lam sach SrC03 va<br /> cac phan tich khac phuc vu cho nghien cim trien khai ung dung [11,12].<br /> Vdi muc tieu dua phuong phap phan tich huynh quang tia X iing dung trong cdng nghiep khai<br /> thac va che bien khoang san, chiing tdi da nghien ciin ehl tao he may PKHQTX cd kich thude<br /> nhd gpn. de sir dung va tien Igi hon he may EDS-XT99. Vdi kinh phi do Vien Khoa hpc va<br /> Cdng nghe Viet Nam cip, diu nam 2010, he may cd ciu hinh tuong tu, model XRF5006-HQ02,<br /> sir dung dau thu tia X lam lanh bang dien da dua vao thir nghiem nhd gpn va tien dung hon<br /> nhieu so vdi he may EDS-XT99 trudc day nhu thiy tren hinh 4. Chit lugng ciia he may nay tuy<br /> chi tuong duong loai trung binh kha ciia thi gidi, nhung phii hgp vdi dilu kien khai thac, sii'<br /> dung trong nude va viec bao tri, sira chira cung nhu chuyin giao thuan tien han rat nhilu.<br /> <br /> <br /> <br /> <br /> Hinh 4: He phd ke huynh quang tia X sir dung ddu thu tia X ldm lanh bdng dien vd ngudn kich<br /> thich mdu bdng den phdt tia X, model XRF5006-HQ02.<br /> <br /> <br /> <br /> <br /> 56<br />  Hoi nghi Khoa hoc ky niem 35 ndm Vien Khoa hoc vd Cong nghe Viet Nam - Hd Noi 10/2010<br /> <br /> <br /> <br />