Detect Contaminant in Oil by TG-IR Analysis

Size: px

Start display at page:

Download "Detect Contaminant in Oil by TG-IR Analysis"

雄广
6 years ago
Views:

1 紫外光 / 可見光分光光譜儀 PerkinElmer 張文昆

2 Content 光譜原理定量原理 Beer Lambert Law 配件介紹應用說明

3 分子光譜學吸收光譜 UV/vis IR 散射光譜 Fluorescence Raman

4 Electromagnetic Spectrum 10nm 200nm 380nm 780nm 波長 2.5 μm 25 μm 50μm 30cm Vacuum UV Near or Quartz UV Visible N I R Infra Red Far-IR to Microwave 波數 4000 /cm 400 /cm 200 /cm

5 光譜原理吸收光譜 - 波長範圍涵蓋紫外光區, 可見光區及近紅外光區分子吸收紫外線及可見光使分子外層的鍵結電子耀遷, 同時亦改變電子的轉動及振動態, 故產生一連串的吸收光譜 1100nm 190nm

6 UV/Vis 光譜形成的基本原理當紫外線或可見光通過單原子粒子或分子可使這些原子或分子之外層電子產生遷移, 故有少數頻率被吸收, 但如 x 射線其頻率較紫外線頻率高, 即有更大能量, 可以使內層電子提昇而發生遷移. 多原子分子除具有電子能 (electronic energy)e e 外, 常有各原子間之振動能 (vibrational energy)e v, 及分子繞質量中心之轉動能 (rational energy)e r. 分子總內能可寫為 :E =E e + E v + E r 分子吸收紫外線及可見光使結合鍵電子激發, 亦改變了振動及轉動態, 故分子之紫外線及可見光譜包括一連串密集吸收帶, 故所得到的光譜為較寬的譜帶.

7 吸收原理有機物的價電子 : ( 鍵結軌域, 基態 ) σ: 電子雲對稱於原子核連線 π: 電子雲平行於原子核連線 n : 單獨屬於某原子而不形成軌道有機物的價電子 : ( 反鍵結軌域, 激發態 ) σ*: 反鍵結軌域 π*: 反鍵結軌域

8 Types of electronic transitions

9 s to s * alkanes( 烷基 ) ~ 150

10 p to p*

11 Chromophore l max alkenes( 烯烴 ) ~ 175 alkynes( 炔烴 ) ~ 170 carbonyls( 羰基 ) ~ 188

12 h to s*

13 Chromophore l max alcohols, ethers( 醇, 醚 ) ~ 185 amines( 胺 ) ~ 195 sulfur compounds ( 含硫化合物 ) ~ 195

14 h to p * carbonyls( 羰基 ) ~ 285

15 Choice of Solvent Solvent Minimum Wavelength (nm) acetonitrile( 乙腈 ) 190 Water( 水 ) 191 cyclohexane( 環己烷 ) 195 hexane( 己烷 ) 195 methanol( 甲醇 ) 201 ethanol( 乙醇 ) 204 ether( 醚 ) 215 methylene chloride( 二氯甲烷 ) 220 chloroform( 氯仿 ) 237 carbon tetrachloride( 四氯化碳 ) 257

16 分子光譜的吸收是带光譜

17 UV 的物理學原理 100% = A% + T% + R% A% = 吸收率 T% = 穿透率 R% = 反射率

18 UV 光學設計光源濾光片分光鏡單光器偵測器

19 Source - 光源 P D2 lamp ( 重氫燈 ) to 326nm P Tungsten ( 鎢鹵燈 ) to 1100nm

20 Source - D2 光源 P 氘燈 (Deuterium lamp): 可使用波長在 180~400nm 左右, 其原理是低壓時氘分子受電子撞擊除外層電子達到激發態並且可使分子分解成原子, 原子可帶走任意大小的動能, 所餘能量不再是定值, 故發射的是連續波長, 其發射圖譜主要在紫外線部分, 但請注意在及 nm 另有兩支尖銳的 peak nm P 儀器開機波長自我校正, 偵測 D2 Peak E nm

21 Source - Tungsten-halogen 光源鹵素鎢燈 (tungsten-halogen lamp) : 為最常見的可見光能源, 能量分佈近於黑體輻射, 適用波長在 310~2500 nm. 通常一般分析儀器的低波長限制在 190 nm, 而非 180 nm 其原因是因為空氣中氧氣的吸收造成的. 而高波長限制在 1100 nm 是受限於偵測器.

22 光柵 (grating) 早期的分光是利用稜鏡, 但因分散能力很差, 且不成線性, 所以目前均使用光柵來分光. 稜鏡現在的 grating

23 分光過程

Achieving expanded range with the Lambda series Source doubling mirror for improved sensitivity Pre-aligned lamps for service ease For ultra-low stray light performance Precise Adjustment of beam

24 Achieving expanded range with the Lambda series Source doubling mirror for improved sensitivity Pre-aligned lamps for service ease For ultra-low stray light performance Precise Adjustment of beam height 4-segment design increases measurement accuracy Second sampling area houses a range of snap-in modules 3D detector module PMT/InGaAs and Pbs detectors for full range scanning 175 to 3300nm Corrects for inherent instrument polarization For sensitive and accurate measurements on highly absorbing samples Largest sample compartment in the Industry

25 分光系統 - Chopper System 雙光束系統 4 階段性 (segment) 設計 : 切換樣品光束及參考光束每兩階段 ( 對樣品光束及參考光束而言 ) 有獨立的歸零作用 How it work?

28 The Beer s Law

29 定量原理 - 比耳定律 (Beer Lambert Law ) I A( l) ( l) * b* c log 0 I = 莫耳吸光係數, M -1 cm -1 b = 光徑長, cm c = 濃度, mole/l I 0 = 入射光強度 I = 穿透光強度 I 0 I b

30 光徑長及濃度對吸收度的影響 1A 2 倍光徑長 ( 濃度固定 ) 2A 1A 2 倍濃度 ( 光徑固定 ) 2A

31 Measured Absorbance 吸收原理 A I log 0 I log T I 0 = 入射光強度 I = 穿透光強度 100% T = 0 A 10% T = 1 A 1% T = 2 A 0.1% T = 3 A 0.01%T =? % Stray Radiation % Stray Radiation % Stray Radiation % Stray Radiation cm True Absorbance

32 The UV/Vis 光譜儀 Accessory

33 液體配件 P 各式液槽 (Liquid Cell Holder) 長光徑槽座 ( Up to 10 cm) 試管槽座圓柱型槽座 P 各式液體樣品槽 Quartz Cell ( 1, 2, 5, 10 cm) 微量 Quartz Cell ( 最小體積 2uL) Flow Cell ( 流動式 )

34 液體配件 Routine 分析利器 Autosampler( 自動取樣器, 最多可容納 180 個樣品 & 20 標準品 ) 8 槽 Cell Changer & 13 槽 Cell Changer 1cm 光徑長 5 槽 Cell Changer 5cm 光徑長

35 液體配件 P 控溫配件水浴式控溫外接循環水槽電子式控溫 25~40 度 & 0~100 度 Temperature Sensor

36 穿透式夾具 - regular sample 0 度入射角夾具 S Optional 0~60 度可變角 0~360 度可變角 Light

37 Specular Reflectance- 相對反射附件 (1) 單一固定角度 : near normal angle 6,45,80 degree 6 degree 45 degree

38 Specular Reflectance- 相對反射附件 (2) 可變角度 : 15 to 70 degree

39 Specular Reflectance- 絕對反射附件 (1) 單一固定角度 (AR / HR) VN type: near normal angle 8,15,30,45,60 degree

40 Specular Reflectance- 絕對反射附件 (2) 單一固定角度 (HR) VW type: near normal angle 7.5

Integrating Spheres Transmission Measurements Use with diffuse transmitting and thick samples Automotive paint films UV blocking Plastics effect of UV blockers Sunglasses protection properties

Absorbtance the % energy not transmitted or reflected. e.g solar panels, coatings, insulation Which sphere? Sphere diameter is often specified in test method e.

41 Integrating Spheres Transmission Measurements Use with diffuse transmitting and thick samples Automotive paint films UV blocking Plastics effect of UV blockers Sunglasses protection properties Architectural, safety, automotive glass UV/Vis and NIR properties Diffuse and Total Reflectance Product appearance color, gloss, haze, translucency, texture of glass, paper, paints/coatings, plastics Absorbtance the % energy not transmitted or reflected. e.g solar panels, coatings, insulation Which sphere? Sphere diameter is often specified in test method e.g ASTM, CIE, ISO protocols 150mm sphere required for absolute color measurements (inter-lab comparisons) 60mm sphere is used for relative measurements 60 mm detector sphere is used with primary sample compartment accessories when there is low energy or lightscattering

42 UV/Vis Application

43 六價鉻檢測原理 - 萃取與溶出萃取 MC x O y H z MO 2 6+ 樣品中之 Cr 6+ 及其化合物消化分解 H 2 O

44 六價鉻檢測原理螯合與量測吸收值波長 Lambda 25 UV/Vis Spectrometer 螯合顯色劑

45 實際測試 - 塑膠製品黃色捆帶黃色膠布 Sampling EPA 7196 A EPA 3060A Digestion Color Development

46 實際測試金屬製品鐵片螺絲 Sampling Lambda Series Leaching Color Development

實際測試 - 檢量線 0.400 0.35 0.30 0.25 A 0.20 0.15 0.10 0.05 0.000 0.000 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.

47 實際測試 - 檢量線 A xe-6g/ml Equation: y = e-01 * x Residual error: Correlation coefficient: Standard Solution

48 Color Filter - 穿透率 %T & CIE 色度計算 Result text Color method spectrum Result graph

cost New manufacturing techniques to lower cost Improvements in efficiencies

49 Renewable Energy Researchw( 太陽能 ) Renewable Energy Research Solar cell Silicon no longer the only source Thin films are being developed to reduce cost New manufacturing techniques to lower cost Improvements in efficiencies is a major current driver Weathering of the materials is an important consideration

50 Integrating Sphere Haze Measurements for Solar cell

51 Integrating Sphere Haze Measurements

52 Integrating Sphere Haze Measurements % Haze = [(T4/T2) - (T3/T1)] x 100% = [(1940/11781) (0.194/40000) =[( )] = %

53 Depolarizer or Polarizer?? 軟體控制的 Double Polarizer / Depolarizer 系統 - 反射或穿透大於 10 度時考量 or 量測 polarizer film 時軟體控制的 Common Beam Depolarizer (CBD) : 190 to 2600nm polarizer 範圍 - crystal : 230 to 2300nm 可作角度的掃描

55 THIN FILM COATINGS Mirrors Interference Filters Short/Long Pass Filters Neutral Density Filters Lenses Reproduced from Melles Griot 1998

56 Architectural Glass 建築玻璃 Reflective Coated Glass Low-E Glass Reproduced from Guardian Industries 1998

of packaging materials Safety and appearance of cosmetics Weathering of coatings used to

57 Sun Protection( 太陽眼鏡 ) Health / Safety Sun protection Skin protection from UVa and UVb Eye protection from the same Degradation of packaged materials from exposure Measurement of packaging materials Safety and appearance of cosmetics Weathering of coatings used to protect everything we touch Specialty surfaces to modify solar energy interactions with us

Cosmetics sample( 化妝品 ) Cosmetics Lip Gloss Reflectance spectra collected with the 150 mm integrating sphere Color Analysis Spectrum Ill Obs CIE X CIE Y CIE Z CIE x CIE y L a b

58 Cosmetics sample( 化妝品 ) Cosmetics Lip Gloss Reflectance spectra collected with the 150 mm integrating sphere Color Analysis Spectrum Ill Obs CIE X CIE Y CIE Z CIE x CIE y L a b STRAWB1.SP D65 10 º GRAPE1.SP D65 10 º DC_RED1.SP D65 10 º

59 Cosmetics sample Cosmetic blush %R Spectra

分子光譜與光電材料的應用光電材料暨檢測研討會分子光譜於光電材料上的應用 2009 Perkin Elmer Tiffany Kang 康瑜容 PerkinElmer Taiwan 珀金埃爾默股份有限公司什麼是分子光譜? Increas

分子光譜與光電材料的應用光電材料暨檢測研討會分子光譜於光電材料上的應用 2009 Perkin Elmer Tiffany Kang 康瑜容 PerkinElmer Taiwan 珀金埃爾默股份有限公司什麼是分子光譜? Increas 光電材料暨檢測研討會分子光譜於光電材料上的應用 2009 Perkin Elmer Tiffany Kang 康瑜容 [email protected] PerkinElmer Taiwan 珀金埃爾默股份有限公司什麼是分子光譜? Increasing Wavelength 50,000 12,820 4000 400 cm-1 Gamma X-ray UV NIR IR