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Group members

Dr. Nor Hasimah Mohamed 2.2 Development of Thorium [email protected] Pn. Nor Azillah Fatimah Othman Adsorbent by Radiation‐induced graft [email protected] Polymerization Pn. Sarala Selambakkannu [email protected]

Dr. Ting Teo Ming [email protected]

Collaborating institute Industrial Wastewater • JAEA Takasaki, Japan sector pollutant • Dr. Noriaki SEKO Iron and Steel BOD, COD, oil, metals, acids, phenol, [email protected] and cyanide Textile and leather BOD, solids, sulfates and chromium Pulp and paper BOD, COD, Solids, chlorinated organic compounds Petrochemical and refineries BOD, COD, mineral oils, phenol ns chromium chemicals COD, organic chemicals, heavy metals, cyanide microelectronics COD and organic chemicals mining Metals, acids and salts

XRF analysis of xenotime RARE Earth Mining 1 Al2O3 Aluminium oxide (2.8%) 17 ThO2 Thorium oxide(0.9%) 2 SiO2 Silicon dioxide (3.4%) 18 UO2 Uranium oxide(1.3%)

3 P2O5 Phosphorus pentaxide (19.7%) 19 CeO2 Cerium oxide(1.2%)

As mining of rare earth metals, used in 4 Cl Chlorine (0.06%) 20 Nd2O3 Neodymium(III) oxide(0.8%) everything from smart phones to wind 5 K2O Potassium oxide(0.2%) 21 Sm2O3 Samarium(III) oxide(0.6%) turbines, scientists warn of the dangers of 6 CaO Calcium Oxide (0.3%) 22 Tb4O7 Tetraterbium heptaoxide(0.4%) 7 TiO Titanium dioxide(14.5%) 23 Dy O Dysprosium(III) oxide(4.4%) the toxic and radioactive waste generated by 2 2 3 8 Cr2O3 Chromium(III) oxide 24 Ho2O3 Holmium Oxide

the mines and processing plants. 9 MnO Manganese(II) oxide(0.7%) 25 Er2O3 Erbium(III) oxide(3.9%)

10 Fe2O3 Ferric oxide(2.4%) 26 Yb2O3 Ytterbium(III) oxide(4.5%)

11 ZnO Zinc oxide(0.06%) 27 HfO2 Hafnium(IV) oxide

12 Rb2O3 Rubidium oxide 28 SO3 Sulfur trioxide (0.6%)

13 Y2O3 Yttrium oxide(43%) 29 WO3 Tungsten trioxide

14 ZrO2 Zirconium oxide(1.2%) 30 Gd2O3 Gadolinium(III) oxide(1.8%)

15 Nb2O5 Niobium pentoxide

16 La2O3 Lanthanum oxide(0.6%)

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Significant effect thorium at low NM pilot plant concentration

Input volume: 100 kg/day of xenotime mineral  thorium: 0.9 kg/day severe radioactive and toxicological effects on living organisms even at very low level.

 thorium in natural water has cumulative effect to marine organism, which is harmful Precipitation techniques from pilot plant: 95% thorium recovery (0.855kg) to aquatic plants and animals. studied by Thorium Flagship group: 2.1 & 2.3

5% discharge into waste: 0.045 kg (45g) Low concentration of thorium

Requirement for high performance adsorption High performance adsorbent . High adsorption rate . High capacity . High selectivity

Can be developed by graft polymerization

List of functional groups and their Graft polymerization selectivity

• Provides a wide range of functional groups onto various types polymer substrates

• Examples: ‐NH2, ‐C=N‐, COOH, ‐SO3H etc.

• Each functional group has a unique chemistry

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Examples of Functionalization functionalization Ring opening reactions of epoxy group

I- • Direct grafting of functional monomer a) OH CH + 3 epoxy group N - + SO Na SO3 Na • Post‐derivatization of graft chains N 3 CH3 H Anion-exchange CH3I O adsorbent Polymer O matrix OH b) - + SO3 Na O CH2=CH Na2SO3 Cation-exchange adsorbent Glycidyl methacrylate COO- Na+ 1.Desired functional group c) OH (GMA) N COO- Na+ NH(CH COONa) 2.Precursor functional group 2 2 Chelating adsorbent

Adsorbent can be fabricated by Therefore selective adsorbent can be radiation‐induced graft polymerization fabricated Farmer

polymer grafting metal ion

Tasteless fruits Deliceous fruits

scientist Electron Beam

grafting Functional group

Ordinary polymer Functional polymer Non selective interaction selective interaction

radiation‐induced grafting method functional Merits of preirradiation‐induced creating group Irradiation graft chains Chemical Trunk polymer radicals Grafting attachment modification grafting

monomer . clean technology Adsorption ion in . solvent free aqueous solution functional . easy handling group . graft controlled grafting degree chain

Graft chain Weight of graft chain [g] 【 】 Degree of grafting (Dg) [%] = ×100 Trunk Polymer Weight of trunk polymer [g] 【 】

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How to control degree of grafting? radiation dose & grafting time Trunk polymer Preliminary study on the “graft chain” 160 radical adsorption of thorium from 140 Trunk polymer irradiation 120 aqueous solution at BTS 100 Radicals (active sites) 80 60 Monomer 40 (grafting) 20 degree of grafting, % % of grafting, degree 0 0 8 16 24 32 40 48 Grafted polymer time, h 30 kGy 50 kGy 100 kGy 150 kGy

Types of trunk polymers for thorium Grafting Method 1 ‐ Emulsion Grafting flagship emulsion

Surfactant Surfactant:Tween 20 Monomer: GMA, MMA Micelle Solvent: Water As a Trunk Polymer Fibrous kenaf fiber non woven fiber (Pn Nur Azillah Fatimah) (Dr Nor Hasimah) adsorbents

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Fig. 1: The Fig.2 : The Fig. 3: pre-pack glass ampoules Nitrogen Fig. 4: trunk were bubbling Monomer Fig. 5: The sealed glass polymer evacuated and of monomer solution was ampoules were ready for EB sealed to solution. added into banana fiber nylon fiber irradiation remove air ampoule. then in a water bath to initiate (Pn Sarala) (Dr Ting) using a vacuum pump. grafting reaction.

Grafting Method 2‐ CVD grafting technique Fig. 1: The Metal ions: Standard solutions pre-pack trunk polymer As an aqueous model for xenotime ready for EB (non‐radioactive Th‐232 & U‐238) irradiation

Monomer feed N2 gas Vaporizer Batch Adsorption test Peristaltic Adsorbent pump Recirculating chiller CVD reactor Sampling Th, U, Dy, Tb, Adsorption Y, Er ion for ICP-MS Vacuum solution analysis pump

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Synthesis of thorium adsorbent with Analytical methods nonwoven PE fiber Electron beam 10‐100 kGy H H Chemical H H grafting modification ( • H H H H C C )n ICP‐MS ( O‐R ( C C )n ( C C ) C C )n n H • H H H O FTIR MMA H CMPO OCH3 OCH O‐R O 3 • FE‐SEM/ EDX Radical O H2C OCH OCH3 OCH3 3 O‐R • Elemental analyzer O CH3 OCH 3 OCH3

MMA = methyl metacrylate CMPO = Octyl(phenyl)‐N,N‐diisobutylcarbamoylmethylphosphine oxide

Selectivity study of thorium with REE FTIR Analysis 200 Adsorbent: (Dg: 300%), 180 NWPE‐g‐MMA 160 Weight: 10 mg, 140 Effect of Metal ion conc.: 10‐200ppb Er, Dy ,Y, Yb, U,Th Solution, 120 Solution volume: 50 mL (pH5), 100 NWPE dose & monomer Temp.: 25Ԩ, Adsorption time: 24h 80 60 800 Conc. (ppb) transmittance 40 10 kGy 176 700 180 20 50 kGy 157 0 600 100 kGy 160 147 400 2400 4400 500 140 127 400 120 ‐1 (%) Dg Wavenumber (cm ) 300 120 103 200 Un‐graftted NWPE 100 78 100 75 Initial pH5 80 0 Graftted NWPE‐300% 0510 60 MMA Conc. (%) 40 24 10 20 1 0 0 Dy‐162 Er‐167 Y‐89 Yb‐173 U‐238 Th‐232

Synthesis of thorium adsorbent with Adsorption of thorium at various concentration Banana adsorbent (Dg: 100%), lignocellulose fiber fibre Weight: 50mg, OH Metal ion conc.: 10‐50ppm Th O Solution, ‐NH(CH2NHCH2)5H electron beam O OH Solution volume: 50 mL (pH 6), 10 kGy chemical O functional ‐NH(CH NHCH ) H Temp.: 25Ԩ, grafting modification 2 2 5 Adsorption time: 3h. group O O O O O O O O O conc. (ppm) O O O O GMA n n n n CH OH CH ỌH CH2OH O 2 OH 50 CH2OH 2 O O R 40 O O O O OH initial O 30 Radical R O O O O OH final Graft O 20 chain R O 10 0.00042 O 0 0 0.00069 0.00079 0 10 20 30 40 50 conc. (ppm)

Grafted with emulsion technique

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Selectivity study of thorium with heavy metal Adsorbent: Weight: 100 mg Kenaf Metal ion conc.: 0.1‐2ppm conclusion fibre Th, U, Al, Cr, Cu Solution, OH O Solution volume: 50 mL (pH2,4,6), Temp.: 25Ԩ, ‐N(C3NH3) O O OH Adsorption time: 30 min Imidazole • Thorium can be adsorbed even at low ‐N(C3NH3) conc. (ppb)O concentration using modified fiber initial pH2 2500 2,038 1,967 2000 pH4 pH6 • High selectivity of thorium as compared to other heavy metal ions at low pH 4‐6 1500 1,135 1,254 1,005 994 1,121 1000 994 500 102 70 87 13 10 55 0 0 28 8 8 50 0 Th‐232 U‐238 Al‐27 Cr‐52 Cu‐63

Grafted with CVD technique

Future plans

To fabricate an imprinted polymer with single ion affinity Thank you for your kind Attention To carry out column mode adsorption

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