FTIR Technology Introduction Tiffany Kang 康瑜容 Product Specialist PerkinElmer Taiwan

利用干涉光譜做傅利轉換( FT(t) ) , 得到有機光譜 應用 : What is FTIR ? 利用干涉光譜做傅利轉換( FT(t) ) , 得到有機光譜 應用 : 利用有機物振動光譜得到官能基 (function group) 及指紋區(fingerprint)光譜 , 做定性及定量分析 Page 2

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IR 原理 Page 4

IR 的原理 IR 的原理是看分子的振動時 吸收光譜,不同的分子振動有不同的吸收,這樣即可輕易得到有機官能基光譜並分析之 Page 5

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IR 的歷史 Page 8

Classical IR Page 9

Fourier-Transform IR Page 10

Why used FTIR ? 非破壞性分析 , 操作簡單 , 分析快速 樣品直接分析 , 幾乎勿需前處理 配合顯微鏡附件 , 可作微小樣品分析 (約 10 um) 配合資料庫搜尋 , 可作未知物分析, 如污染物, 新材料開發 可利用化學官能基強度或光譜特性變化 , 來做定量分析 無需化學試劑 , 無環境污染問題 , 安全無污染 Page 11

傅立葉轉換成IR光譜 Page 12 8

傅利葉轉換:扣除background, ratio得到樣品光譜 穿透光譜 80.8 60 Ratio %T EGY 40 Sample 樣品掃瞄 20 0.3 4400.0 2000 1000 450.0 cm-1 4400.0 2000 1000 450.0 cm-1 Page 13 9

FT-IR Spectrometer 干涉儀 Page 14

The steps necessary for method development are shown here The steps necessary for method development are shown here. This represents method development starting from the very beginning. Most method development starts with an existing method, which is then modified. This is generally easier and is preferred if a method exists that is similar to what is desired. FTIR 穿透量測模式介紹

FTIR Transmittance measurement 固體穿透式技術      - Mull Cell法 - KBr鹽片法   - Cast Films分析法    - Hot Pressed Films分析法    - Beam Condenser法   液體樣品技術 氣體樣品技術 Page 16 15 16

Solid transmittance accessories Mull Cell法 適用於 : 可被磨成細粉末之樣品 會與KBr產生離子交換現象，無法使用KBr Disk 配件內容: - 使用液狀蠟油 a) Nujol（礦物油1350cm-1） b) Fluorolube（氟化礦物油40001350cm-1） 使用配件  a) 瑪瑙研砵及杵 d) 圓形KBr鹽片 b) 礦物油  e) 可拆式Cell Mount c) 刮刀   Page 17 15 16

Solid transmittance accessories Mull Cell法 Page 18 15 16

Window materials   Page 19 15 16

Window materials   Page 20 15 16

Solid transmittance accessories KBr 鹽片法 可使用之基質包括 : KBr, KCl, NaCl, KI, CsI 及 PE powder  配件內容: a) 瑪瑙研砵及杵（自動磨碎機）   b) 光譜級KBr粉末   c) 紙墊片   d) 13mm鑄模（die）   e) 15ton油壓打碇機   f) 13mm 鹽片固定器 Page 21 15 16

Solid transmittance accessories KBr 鹽片法 Page 22 15 16

Solid transmittance accessories Cast Films分析法 塑膠粒或不規則型高分子無法直接使用穿透分析方式，但可使用適當溶劑將之溶解，再滴在鹽片上，溶劑揮發後形成薄膜而進行分析。 Page 23 15 16

Solid transmittance accessories Hot Pressed Films分析法 熱壓成膜分析技術一般用於大於或不規則的高分子，將樣品加熱熔融成液狀再加薄膜，可藉由constant thickness film maker來固定膜厚，然後放在磁性薄膜固定器上分析。 Page 24 15 16

Solid transmittance accessories Beam Condenser分析法 光濃縮配件可將IR光束經鏡頭濃縮，增加其光的密度，一般有4X, 5X, 6X，以5X最常用。 適合樣品:   - 微小的樣品 - 寶石鑑定 Page 25 15 16

Liquid transmittance accessories 液體樣品槽分為: - 可拆卸式液體樣品槽 - 固定式液體樣品槽  一般液體樣品槽必須含有: 1.  樣品槽本體 2.  鹽片, 可分為不防水鹽片，如NaCl, KBr及防水鹽片，如 CaF2, AgBr, KRS-5 3.  Spacer, 分為0.1mm~0.015mm間，一般為鐵弗龍材質， 也有使用銅、鉛材質 Page 26 15 16

Liquid transmittance accessories 可拆卸式液體樣品槽 固定式液體樣品槽 Page 27 15 16

Gas transmittance accessories Gas Cell 一般為10cm固定光徑長，適用於pure gas   Long Path Gas Cell 使用光的折射方法，使光徑變長，長度可 達100公尺適用於低含量的氣體分析 Page 28 15 16

Heatable transmittance accessories Heatable accessories 利用循環方式或電子式加熱, 使樣品於某特定溫度下量測IR光譜, 固態, 液態及氣態均有適合配件  內容包含: - Cell (Liquid or Gas)或 Clip (for solid) - Heating Jacket - Temperature controller or Water circulator Page 29 15 16

The steps necessary for method development are shown here The steps necessary for method development are shown here. This represents method development starting from the very beginning. Most method development starts with an existing method, which is then modified. This is generally easier and is preferred if a method exists that is similar to what is desired. FTIR 反射量測模式介紹

FTIR 反射量測模式 Specular Reflectance (正反射) -- 表面光滑面 Specular Absorption Reflection (正吸收反射) Specular Reflection (正反射) -- K.K convert Grazing Angle Reflectance -- 可量測約幾十個 A Diffuse Reflection (散射反射) -- K.M convert --表面粗糙面 Powder (KBr dilute) SiC pad A Total Reflectance (ATR 全反射) --表面 0.2 - 6 um The steps necessary for method development are shown here. This represents method development starting from the very beginning. Most method development starts with an existing method, which is then modified. This is generally easier and is preferred if a method exists that is similar to what is desired. Page 31

Specular Reflectance (正反射量測) Grazing Angal (擦角反射附件) 應用 : 樣品表面光滑 FTIR 反射量測模式 I Specular Reflectance (正反射量測) Grazing Angal (擦角反射附件) 應用 : 樣品表面光滑 Page 32 38

Reflection Absorption 正吸收反射 樣品表面需光滑面 , 入射角 = 反射角 可改變入射角角度 , 來增加 IR 吸收強度 Grazing Angle Reflectance -- 80-85 度 , 可量測約分子層之厚度, 光束會變大, IR 光能量減弱 , 需與偏光鏡配合使用 有機物 金屬 Page 33 15 16

Reflection Absorption of Coatings 正吸收反射 100 200 2000 1800 1600 1400 1200 1000 800 600 Wavenumber (cm-1) Epoxy coating on Al - near normal reflectance Cured at 100c overnight Difference Page 34 14 17

Specular Reflection 正反射 5% 100% 樣品表面光滑面有機物 95% 穿透 , 5%反射 Dependent upon refractive index (n) and absorptivity (k) Corrected using Kramers-Kronig (KK) 表面光滑的有機物 95% Page 35 18 18

Specular Reflectance of UV Curable Resin After KK %T DR on SiC 3500.0 3000 2000 1500 1000 450.0 cm-1 Page 36 19 19

Glazing Angle Reflectance Page 37 15 16

Diffuse Reflection 散射反射 II Powder Sample SiC pads Kubelka-Munk(K-M) = (1-R∞)2/2 R∞ =2.303ac/s 應用 : 樣品表面粗糙面樣品 Page 38 38

Diffuse Reflection (散射反射) 光路圖 應用於表面粗糙面樣品 亦可利用 SiC 來分析樣品表面的 Coating 得到約 5-8% IR 光強度 The steps necessary for method development are shown here. This represents method development starting from the very beginning. Most method development starts with an existing method, which is then modified. This is generally easier and is preferred if a method exists that is similar to what is desired. Page 39

Diffuse Reflectance 散射反射 得到粉末樣品的反射及繞射(scattering)光譜 得到樣品表面及內部的信號 得到寬廣角度反射光線 為了提高信號強度 , 樣品面積較小 Page 40 20 20

Diffuse Reflectance 散射反射 Page 41 20 20

Diffuse Reflectance of Flame Retardant DRIFTS With KM %T KBr Disk 4400.0 3000 2000 1500 1000 450.0 cm-1 Page 42 22 22

Attenment Total Reflectance ATR 全反射 III Dp= /2 nc [ sin2- (ns/nc)2 ] 1/2 影響分析深度參數有 : 折射率 (R.I) , 入射角度() , 波長() 應用 : 樣品表面分析 (0.2 - 6 um) Page 43 38

全反射 (ATR) 樣品與高折射率之晶體緊密接觸 IR 光譜從樣品表面通過 信號強度依接觸程度 , 反射次數 , 晶體材料有關 IR Crystal Page 44 30 23

ATR Crystals Page 45 30 23

Dp= /2 nc [ sin2- (ns/nc)2 ] 1/2 Horizontal ATR (HATR) Sample IR Metal plate 100% 20-30% to Detector Dp= /2 nc [ sin2- (ns/nc)2 ] 1/2 Page 46 32 24

Horizontal ATR (HATR) Page 47 32 24

高壓單點 ATR 45°single reflection type IIa diamond in tungsten carbide diamond mount Purgeable in-compartment design Fully enclosed beam condensing lens system Unique swing bridge sample platform access Sapphire anvil for high pressure contact Silicon ATR element 3mm diameter Effective sampling area < 0.5mm Page 48 26

Polymer Verification 3800 3400 3000 2600 2200 1800 1400 1000 60 80 100 Poly (ethylene 25% vinyl acetate) for verification Poly (ethylene 25% vinyl acetate) standard spectrum cm-1 %T Page 49 33 25

FTIR Application

應用 橡膠塑膠分析 添加劑判斷 OH Number分析 組成分析 Page 51

Standard spectrum Page 52

Standard spectrum Page 53

光譜比對 Page 54

比對結果 Compare - 980825041.sp File: Correlation: Factor: Comments: pur.sp 0.9988 0.9599 PU rubber 98120814.sp 0.1056 0.3726 Nylon 66 98120816.sp 0.0563 0.1553 PP 98120815.sp 0.0402 0.2428 PC sir.sp 0.0388 0.0916 Si rubber Page 55

原料管制 Page 56

染料組成 Page 57

膠片的品管 Page 58

Cure 的消長 Page 59

PI spectra Page 60

酯基變化 Page 61

OH number Standard x 45m x 45m02 x 45m04 x 45m03 x nv0160~1 x nv0460~1 91.3 85 80 x 45m x 45m02 x 45m04 x 45m03 75 70 65 x nv0160~1 x nv0460~1 x nv0260~1 x nv0360~1 60 Estimated 55 50 x nv0160% x nv0460% x nv0260% x nv0360% 45 40 35 30 x nv0150% x nv0250% x nv0350% x nv0450% 25 x nv0445% x nv0145% x nv0245% x nv0345% 19.5 23.0 25 30 35 40 45 50 55 60 65 70 75 80 85.7 Specified Page 62

檢量結果 Spectrum Quant+ v4.51 PREDICTION RESULTS PCR+ Comment Sample NV0150% OH 30 Calc.Name R_NV050%.SP Normalization None Method 119OH.MD Ver: 2 ID: 1815 Date 02-Apr-2001 09:59: * -------------------------------------------------------------------- * Property Calc.Value Property_1 29.94 Page 63