SEMI AMC TF2 微污染防治專案為提升國內微污染量測之技術水平, 特舉辦離子層析儀之原理教學與儀器參訪活動, 邀請 AMC TF2 成員參加, 期盼讓 SEMI 會員對於離子層析技術於微汙染防治之儀器功能及未來之應用有進一步的認識 以實作參訪及教學模式, 使 SEMI 會員深刻瞭解離子層析技術之概念與原理, 並於活動中結合產業專家, 進行研討, 提出未來應用與發展方向之建議 參訪日期 中華民國 103 年 12 月 11 日 ( 星期四 ) 下午 1:30 ~ 3:30 報名日期 103 年 12 月 4 日至 103 年 12 月 10 日止 主辦單位 SEMI Taiwan 高科技廠房設施委員會奈米微污染控制工作小組 協辦單位 台灣賽默飛世爾科技股份有限公司 報名方式 本參訪活動由郭啟文先生負責報名信箱 : cwkuoj@tsmc.com / 0988935753
Ion Chromatography Introduction & New Technology 台灣賽默飛世爾科技股份有限公司
CHROMATOGRAPHY Eluent( 移動相 ) Eluted slowly Eluted with middle speed Eluted quickly 固定相 3
Mechanism of Ion Exchange Separation Temporal course CO 2 3 3 CO 2 3 3 CO 2 3 CO 2 3 3 3 3 3 3 CO 2 3 3 CO SO 2 34 3 CO 2 3 3 Cl 3 3 CO 2 3 SO 2 4 CO 2 3 Cl 3 CO 2 3 3 SO 2 4 CO 2 3 3 CO 2 3 3 3 Cl 3 3 CO 2 3 3 SO 2 4 CO 3 2 3 CO 2 SO 3 4 CO 3 2 3 CO 2 3 3 Cl 3 3 CO 2 3 CO 2 3 3 Cl 3 CO 2 3 3 3 3 CO 2 3 SO 2 4 3 3
Example of Anion Measurement ms 8 F NO 2 Cl NO 3 SO 4 2 Br HPO 4 2 0 0 2 4 6 8 10 12 14 16 Retention time(min) 5 Proprietary & Confidential
Example of Cation Measurement µs 4 3 2 K NH 4 Na Mg 2 Ca 2 1 0 0 2 4 6 8 10 12 14 Retention time (min) 6
Basic Flow diagram of IC Eluent Column Detection cell F Cl Pump Sample injection valve Suppressor NO 2 NO 3 SO 2 4 Br HPO 2 4 Detector Injection Pumping Separation Detection Recording 7
RFIC EG H 2 0 Data Manageme nt HighPressure NonMetallic Pump Eluent Generator (OH or H ) Detection Waste Sample Inject * No external eluent (Autosampler) No external regenerant Suppressor Conductivity Detector Recycle Mode 8 Proprietary & Confidential
IC Concentrator design Equilibrium Injection Position Concentration Load Position Analysis Injection Position Injection Valve Waste Eluent Conc. column Sampling pump (start) To separate part Sampling pump (pumping) Sampling pump (stop) 9 Proprietary & Confidential
Superficial Anion Exchanger DVB Crosslink H 2 C CH 2 CH CH 2 CH CH 2 CH CH 2 CH CH 3 (CH 3 ) 3 NCH 2 Cl (CH 3 ) 3 NCH 2 Cl C H CH 2 CH CH 2 CH CH 2 CH CH 2 (CH 3 ) 3 NCH 2 Cl (CH 3 ) 3 NCH 2 Cl Functional Group 10 Proprietary & Confidential
Ion Exchange Resin ( 樹脂 Latex type) SO 3 N R 3 N R 3 N R 3 SO 3 N R 3 N R N 3 R 3 SO 3 N R 3 N R 3 N R 3 N R 3 SO 3 N R 3 N R3 5μm 11 Proprietary & Confidential
Ion Exchange Resin ( 接枝 Grafted type) COO HPO 3 COO COO HPO 3 COO COO HPO 3 COO HPO 3 COO HPO 3 COO HPO 3 HPO 3 COO 12 Proprietary & Confidential
Functional Groups Detected with Suppressed Conductivity Suppressed Conductivity Detection Carboxylic O RCOH Sulfates O ROSOH O Sulfonates O RSOH O Phosphates O ROPOH OH Phosphonates O RPOH OH 1 Amines RNH 2 2 Amines R RNH 3 Amines R RNR Inorganic Anions e.g., F _, CI _, NO 2 _, NO3 _, SO 4 2 _, PO 4 3 _, I _, Br _, CIO 3 _, SCN _, S 2 O 3 2 _ Inorganic Cations Alkali Metals: Li, Na, K, Rb, Cs, Alkaline Earths: Mg 2, Ca 2 Sr 2, Ba 2 2, Ammonia: NH 4 4 Amines R 4 N 13 Proprietary & Confidential
Role of Suppressor Conductivity ~ NaF,NaCl,NaNO 3 Na 2 HPO 4,Na 2 SO 4 Back Ground: Na 2 CO 3 / Na 3 (700μS) Retention time Conductivity ~ NaF NaCl NaNO 3 Na 2 HPO 4 Na 2 SO 4 Back Ground: Na 2 CO 3 / Na 3 (700μS) Retention time Waste Conductivity HF HCl HNO 3 H 3 PO 4 H 2 SO 4 Back Ground: H 2 CO 3 (15μS) Retention time 14 Proprietary & Confidential
抑制作用 Increase the conductivity of analytes: Raise sensitivity 陰離子 Na / K, Cl H, Cl 陽離子 Na, Cl /SO 2 4 OH, Na Decrease the conductivity of BG (Eluent) : Reduce noise 陰離子 陽離子 Na, 3 H 2 CO 3 (Carbonate 系統 ) Na, OH H 2 O (Hydroxide 系統 ) MSA, H H 2 O 15 Proprietary & Confidential
Microbore 2mm Ammonium 10 ml preconcentration volume, CS12A 16 Proprietary & Confidential
Microbore 2mm Anion 20 ml preconcentration volume, AS17 with CRD 0.300 1 Autoprep AS17,2mm #1 1 ppt ECD_1 2 Autoprep AS17,2mm #2 5 ppt ECD_1 3 Autoprep AS17,2mm #3 10 ppt ECD_1 ìs Fluoride Sulfate 0.200 Nitrite Nitrate Phosphate 0.100 Chloirde Bromide 321 0.050 min 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 Produced by: Dionex Korea Application Lab 17 Proprietary & Confidential
New Technology Capillary HPIC Dedicated High Pressure IC The benefits of speed without compromising resolution; 24/7 uptime of Capillary IC and detection choices in a compact, integrated system 18 18 Proprietary & Confidential
Sensitivity Column ID Flow rate Sensitivity 4.0 mm 1.0 ml/min S/N = 1 0.4 mm 10 µl/min S/N = 100 S/N = 1 S/N = 100 19 Proprietary & Confidential
Conductivity [µs] Sensitivity 16.0 Capillary IC with 0.4 µl Injection 1 Volume Sodium Lithium All with same injection volume Ammonia Potassium Magnesium Calcium 0.4 mm 2.0 16.0 Microbore IC with 0.4 µl Injection Volume Sodium Potassium Lithium Ammonia Magnesium Calcium 2 mm 2.0 16.0 Standard bore IC with 0.4 µl Injection Volume Sodium Potassium Lithium Ammonia Magnesium Calcium 4 mm 2.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 15.0 Retention Time [min] 20 Proprietary & Confidential
New High Efficiency Dionex IonPac 4µm Capillary IC Columns Ionexchange columns with 4 µm particlesize Benefits Smaller particles provide better performance Faster run times with higher flow rates using 150 mm columns Better resolution with standard flow rates using 250 mm columns Applications Anions in environmental waters 5.5 Organic acids in foods and beverages µs Amines in chemical process solutions SEM Image of 4 µm Supermacroporous Bead Fast Run using the High Resolution using the High Resolution using the Dionex IonPac AS184µm Dionex IonPac AS11HC4µm Dionex IonPac CS194µm I o n C h r o m a t o g r a p h y R e a g e n t F r e e I C C a p i l l a r y I C C h r o m e l e o n D a t a S y s t e m 10 µs 0.5 1 0 0 Minutes 3 0 Minutes 40 0 Minutes 40 Improved Resolution Provides Faster Runs and Better Results 5 µs 21 Proprietary & Confidential
Separation of Inorganic Anions using the Dionex IonPac AS184µm Column at Different Flow Rates 20 µs 30 µl/min, 4141 psi 1 2 20 µl/min, 2875 psi 3 4 5 6 10 µl/min, 1508 psi 7 Column: Dionex IonPac AG184µm/AS18 4µm, (0.4 x 150 mm) Eluent Source: Dionex KOH Capillary Cartridge Eluent: 30 mm Col. Temp.: 30 C Inj. Volume: 0.4 µl Detection: Suppressed Conductivity, Dionex ACES 300 Peaks: 1. Fluoride 0.2 mg/l 2. Chloride 1 3. Nitrite 1 4. Sulfate 1 5. Bromide 1 6. Nitrate 1 7. Phosphate 2 15 5 Minutes 10 22 Proprietary & Confidential
Speed Separation of inorganic anions using a 4 µm column at different flow rates. 20 µs 15 30 µl/min, 2820 psi 25 µl/min, 2430 psi 20 µl/min, 2030 psi 15 µl/min, 1570 psi 5 Minutes Column: 10 µl/min, 1140 psi 10 Thermo Scientific Dionex IonPac AS184 µm, 0.4 150 mm Eluent Source: Dionex EGCKOH (Capillary) Eluent: 30 mm KOH Col. Temp.: 30 C Inj. Volume: 0.4 µl Detection: Suppressed Conductivity, Thermo Scientific Dionex ACES 300 Sample: Anion Standard Solution mg/l Peaks: 1. Fluoride 0.2 2. Chloride 1 3. Nitrite 1 4. Sulfate 1 5. Bromide 1 6. Nitrate 1 7. Phosphate 2 Faster run times without sacrificing resolution 23 Proprietary & Confidential
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