熱分析技術 簡介 (dsc, tga & dma)
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熱分析技術 簡介熱分析技術 簡介(DSC, TGA & DMA)(DSC, TGA & DMA)
熱分析技術 簡介熱分析技術 簡介(DSC, TGA & DMA)(DSC, TGA & DMA)
PerkinElmer Thermal Specialist
康瑜容 Tiffany Kang
Tiffany.Kang@perkinelmer.com
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Thermal-Thermal-22
Differential Scanning Calorimetry (DSC)
Thermogravimetric Analysis (TGA)
Thermomechanical Analysis (TMA)
Dynamic Mechanical Analysis (DMA)
常用的熱分析方法
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Thermal-Thermal-33
常用的熱分析方法
DSC Heat flow vs. Temp
- Tm, Tc, Tg
- H, curing time, curing degree
- Reaction rate, kinetics
TGA Weight Loss vs. Temp
- Decomposition temperature
- %Wt percentage
- Oxidative time
TMA Dimensional Change vs. Temp - CTE (1, 2)- Tg- Softening point
DMA Viscoelastic property vs. Temp
- Storage/Loss/Complex Modulus (E’, E”, E*)
- tan - Viscosity and master curve
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Thermal-Thermal-44
高分子材料結構
Type of Polymer Chain Structure
Type Structure ExampleType Structure Example
LinearLinear
Branched Branched short chainshort chain
Long chain Long chain branchingbranching
LadderLadder
Poly(vinyl chloride), PolystyrenePoly(vinyl chloride), Polystyrene
PolypropylenePolypropylene
PolypropylenePolypropylene
Poly(imidazol pyrrolones)Poly(imidazol pyrrolones)
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Thermal-Thermal-55
高分子材料結構
Type of Polymer Chain Structure (Continued)
Type Structure ExampleType Structure Example
StarStar
NetworkNetwork
Interpenetrating Interpenetrating network (IPN)network (IPN)
Phenol-formaldehyde resinsPhenol-formaldehyde resins
Two crosslinked polymers not Two crosslinked polymers not bonded to each otherbonded to each other
Crosslinked epoxy with vinyl Crosslinked epoxy with vinyl polymerpolymer
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Thermal-Thermal-66
高分子材料的分類
Polystryene
Polycarbonate
Polyurethanes
Polysulfone
Amorphous
LOW/MEDIUM
Nylon
PET
Acetal
HIGH
PPS
PP
HDPE
Crystalline
Thermoplastics(No chemical change on heating)
Epoxies
Polyimides
Polyesters
Phenolics
Uncured
Rubber
Silicones
Neoprene
Epoxy
Cured
Thermosets(Chemical change on heating)
Polymers
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Thermal-Thermal-77
Amorphous vs. Crystalline?
Amorphous Amorphous ThermoplasticThermoplastic
Crystalline Crystalline PolymerPolymer
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Thermal-Thermal-88
Semi-Crystalline Polymer
Semi-Crystalline Semi-Crystalline PolymerPolymer
Semi-crystalline polymers contain both amorphous AND crystalline phases
Properties dominated by both Tg and Tm
Semi-crystalline polymers can exhibit additional crystallization during heating
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Thermal-Thermal-99
Thermosetting Polymer
UNCURED PARTIALLY CURED TOTALLY CURED
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Thermal-Thermal-1010
Schematic Results in Thermal Analysis
Quality of sample process DSC(ExQuality of sample process DSC(Ex) TGA TMA DMA ) TGA TMA DMA
-CrystallineCrystalline
-Semi-crystallineSemi-crystalline
-Amorphous-Amorphous
-Semi-crystalline-Semi-crystalline
-General-General
-Liquid-Liquid
-Unspecific-Unspecific
-Solid Melting-Solid Melting
RecrystallizationRecrystallization
SublimationSublimation
Solid-solid transitionSolid-solid transition
Glass transitionGlass transition
Softening without TgSoftening without Tg
Post-crosslinkingPost-crosslinking
DecompositionDecomposition
Ligand releaseLigand release
EvaporationEvaporation
Chemical reactionsChemical reactions
Determination of %Determination of %
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DSC TechniqueDSC TechniqueDifferential Scanning Differential Scanning
CalorimetryCalorimetry
DSC TechniqueDSC TechniqueDifferential Scanning Differential Scanning
CalorimetryCalorimetry
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Thermal-Thermal-1212
Question?
PE 分成 HDPE, LLDPE 及 LDPE - 結構有何不同 ? - 性質有何差異 ? - 結構和性質有何關聯性 ?
結晶的過程為何 ? 加工條件對結晶有何影響 ? 結晶度對透明度的影響 ? 添加劑的影響 ?
DSC 可解決哪些問題 ?
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Thermal-Thermal-1313
What is DSC ?
示差掃瞄熱卡量計 ( Differential Scanning Calorimeter ) :
將樣品置於特定氣氛之下改變其溫度環境或維持在一固定溫度之中去觀察樣品其能量變化,當樣品發生熔融、蒸發、結晶、相轉變等物理現象,或化學變化時,圖譜中將會出現吸熱或放熱帶,進而可推測樣品之性質。
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Thermal-Thermal-1414
Thermal Analysis applications - DSC
- Principle:Principle:
Heat flow change vs. temperatureHeat flow change vs. temperature
- Measures:Measures:
Phase transition (Tg, Tm, Tc) and heat Phase transition (Tg, Tm, Tc) and heat
Curing reaction and other chemical reactionsCuring reaction and other chemical reactions
Diamond DSCDiamond DSC
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Thermal-Thermal-1515
Polymer Transitions
HeatFlow
Temperature
Tg
StressRelief
OrderingProcess
Cold Crystallization
Curing
Tm
Degradation
Start upTransient
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Thermal-Thermal-1616
DSC Thermal Curve of PET
吸
熱
放
熱
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Thermal-Thermal-1717
DSC for curing studies
Detection of Tg Onset of cure Maximum rate of cure (peak maximum) End of cure Heat of cure
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Thermal-Thermal-1818
DSC 熱示差掃描分析儀之應用
相變化點 Phase Transition 熔融熱 H
玻璃轉移溫度 Tg 反應熱 H
熔點 Melting point 活化能 Ea
冷結晶溫度 Crystal Temperature 氧化導引時間 O.I.T.
降溫結晶溫度 Cold Crystal Temperature
反應動力學 Dynamic
結晶度 Crystallinity 交連 Curing
結晶熱 Crystal Energy 純度 Purity
結晶半週期 Crystal Period 比熱 Cp
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Thermal-Thermal-1919
DSC 的設計方式
熱流式 熱流式 Heat Flux DSCHeat Flux DSC 熱補償式 熱補償式 Power Compensation DSCPower Compensation DSC
-量測量測 TT
- 由由 H = kH = kTT 計算計算 HH
- 爐體較大爐體較大
-直接量測直接量測 HH
- 不需複雜數學運算不需複雜數學運算- 爐體較小爐體較小
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TGA TechniqueTGA TechniqueThermogravimetric AnalyzerThermogravimetric Analyzer
TGA TechniqueTGA TechniqueThermogravimetric AnalyzerThermogravimetric Analyzer
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Thermal-Thermal-2121
Thermal Analysis applications - TGA
Pyris 1 TGAPyris 1 TGA
- Principle:Principle:
Weight change vs. temperatureWeight change vs. temperature
- Measures:Measures:
Compositions and wt%Compositions and wt%
Thermal stability and decomposition temp.Thermal stability and decomposition temp.
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Thermal-Thermal-2222
TGA Design Concept
懸吊式懸吊式 水平式水平式 上置式上置式
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Thermal-Thermal-2323
TGA Thermal Curves
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Thermal-Thermal-2424
主要元件 p Temperature control device
- Furnace, Thermocouple
p Weight measurement device
-Null Balance
Detector
Tare WeightSample
Torque Motor
TGATGA 的設計原理的設計原理
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Thermal-Thermal-2525
TGA 熱重分析儀
水份含量 溶劑含量 塑化劑含量 高分子添加物含量 裂解溫度 灰份含量 無機添加物含量 氧化導引時間測量
TGA-FTIR/TGA-MS 熱穩定測量 不穩定材質測試 異味材質測試 添加物種類測試
TGA-GC/MS 未知物種類判斷 混合溶劑判斷
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Thermal-Thermal-2626
TGA for compositional analysis
Molding compound contains epoxy and filler
Epoxy can be burned off and residue is inert reinforced filler
TGA provides accurate and reproducible compositional data on molding compound
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TMA/DMA TechniqueTMA/DMA TechniqueMechanical AnalyzerMechanical Analyzer
TMA/DMA TechniqueTMA/DMA TechniqueMechanical AnalyzerMechanical Analyzer
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Thermal-Thermal-2929
Thermal Analysis applications – DMA/TMA
DMA 8000DMA 8000
- Principle:Principle:
Viscoelastic properties vs. temperature (DMA)Viscoelastic properties vs. temperature (DMA)
Dimensional change vs. temperature (TMA)Dimensional change vs. temperature (TMA)
Measures:Measures:
Glass transition pointGlass transition point
Storage, Loss modulus and tan delta Storage, Loss modulus and tan delta
Coefficient of thermal expansion (CTE)Coefficient of thermal expansion (CTE)
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Thermal-Thermal-3030
What is DMA ?
DMA (Dynamic Mechanical Analyzer)
動態黏彈機械分析儀 將樣品置於特定環境下,偵測樣品在溫度、力量、或頻率改變下,其機械性質變化的情形,進而判定材料的特性。
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Thermal-Thermal-3131
材料的黏彈性質…
E’ – Storage Modulus
儲存模數 彈性性質
E”– Loss Modulus
損失模數 黏性性質
tan = E” / E’
E”
E’
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Thermal-Thermal-3232
黏彈機械性質 ex. 模數 (Modulus), 黏度 (Viscosity), 阻尼相 (tan ) …
微小的相變化 ex. - transition, Tg 以 DSC/TMA 測量不易者 … 活化能 (Activation Energy) 計算
預測材料使用壽命 ex. Creep Recovery, Time-temp. superposition …
模擬製程中材料及環境變化 ex. Curing process, controlled humidity, Solvent Immersion …
什麼時候您需要 DMA …
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Thermal-Thermal-3333
黏性
彈性
o
time
o
time
o
time
= 0
= 90
o
o
o
time
o
k
DMA 即為利用 Sine Wave 震盪方式 , 測量回應的分析儀
材料的黏彈性質…
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Thermal-Thermal-3434
Idealized DMA Scan
E’/
Pa
Temperature /K
Tm - melting (1)
Rubbery Plateau (2)
T or Tg
(6)local bend side gradual large chainmotions and groups main scale slippage
stretch chain chain
Rubbery plateau is related to Me between crosslinks or entanglements.
For thermosets, no Tm occurs.
Beta transitions are oftenrelated to the toughness.
Tg is related to Molecular massup to a limiting value.
For purely crystalline materials, no Tg occurs.
In semicrystalline polymers,a crystal-crystal slip, T* occurs.
Tll in some amorphouspolymers
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Thermal-Thermal-3535
Frequency effects things too
Transitions shift Behavior changes
0.0
0.5
1.0
50 75 100Temperature (C)
Tan
Delta
Tan Delta 0.1HzTan Delta 0.316 HzTan Delta 1.0 HzTan Delta 3.16 HzTan Delta 10.0 HzTan Delta 31.6 Hz
Frequency
E’
Morefluid
Moreelastic
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Thermal-Thermal-3636
So frequency can act like temperature
Frequency
E’
Temperature
E’
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Thermal-Thermal-3737
DMA 連結 ...
材料結構特性
製程加工特性
成品特性Molecular weightMW DistributionChain BranchingCross linkingEntanglementsPhasesCrystallinityFree VolumeLocalized motionRelaxation Mechanisms
StressStrain
TemperatureHeat HistoryFrequencyPressureHeat set
Material
Behavior
Dimensional StabilityImpact properties
Long term behaviorEnvironmental resistance
Temperature performanceAdhesion
TackPeel
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Thermal-Thermal-3838
DMA 是如何運作的 ?
Storage Modulus
Loss Modulus
Static Force
Dynamic Force
Frequencyf
Amplitude K
PositionHold Sample
Phase
Thermocouple
Total Force
LVDT
Furnace Options from -190 to 600 C
Force motor
Fixtures
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Thermal-Thermal-3939
多樣化的夾具選擇
Options:
Single Cantilever
Dual Cantilever
3 Point Bending
Tension
Compression
Shear
Quartz Shear
Material Pocket
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Thermal-Thermal-4040
Exclusive Material Pockets
Applications
• Powders like drugs, excipients, foods, natural products, etc.
• Gels
• Uncured adhesives
• Coatings
• Samples that can’t support their own weight
Pocket open Sample in Pocket Pocket closed & sealed
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Thermal-Thermal-4141
DMA mode for mechanical properties change
This plot shows DMA results (E’ and tan delta) for cured substrate
DMA gives the most sensitive measure of Tg
DMA results show that substrate is incompletely cured as 2 split peak was found in tan delta around Tg
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Thermal-Thermal-4242
DMA most sensitive indicator of cure
This plot shows DMA results on completely cured and slightly under-cured PCB’s
Under-cured PCB exhibits a slight increase in E’ above Tg making the board unacceptable
Modulus
(E’)
25 Temperature (C) 250
DMA Results onPCB’s
Good and Bad
Rejected
Acceptable
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Thermal-Thermal-4343
TMA mode for dimensional change
Plot shows results on TMA expansivity of substrate
1st heat shows that the board contains built in stresses as a result of processing
Stresses are released at Tg 2nd heat shows classic TMA Tg free
of stress relief effects
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Thermal-Thermal-4444
更多熱分析的應用更多熱分析的應用……
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高分子熱性質量測高分子熱性質量測高分子熱性質量測高分子熱性質量測
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Thermal-Thermal-4646
高分子的 Tg 分析 -- 加熱歷史的差異
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Thermal-Thermal-4747
結晶測試 -- 恆溫結晶
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Thermal-Thermal-4848
交連測試 交連測試 ---- 升溫交連升溫交連
Epoxy Resin
T (oC)
40 80 120 160 200 240 280
Endothermic
Hea
t F
low
(m
W)
Run 1
H
Run 2 113.3 oC
62.8 oC
30 mw20 oC/min32.76 mg
Range:Heating Rate:Weight:
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Thermal-Thermal-4949
交連測試 交連測試 ---- 恆溫交連恆溫交連
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Thermal-Thermal-5050
交連測試 交連測試 ---- 交連度的影響交連度的影響
DSC Heat Flow
Temperature
DSC Tg As Function of Cure
Less Cured
More Cured
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Thermal-Thermal-5151
交連測試 交連測試 ---- 交連度的影響交連度的影響
DSC Heat Flow
Temperature
Decrease in Cure Exotherm As Resin Cure
Increases Less Cured
More Cured
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Thermal-Thermal-5252
填充物 Filler
常用的填充物 吸水性 環氧樹脂 二氧化矽 碳黑 玻璃纖維
填充物的功能填充物的功能 降低熱膨脹係數降低熱膨脹係數 增高熱導係數增高熱導係數 增加尺寸安定性增加尺寸安定性 降低成本降低成本 改變密度改變密度 改變黏度改變黏度 -- 方便加方便加
工工 降低吸水性降低吸水性
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Thermal-Thermal-5353
碳黑 (Carbon) 含量分析
碳黑經常用來與塑膠混合以改進其化學或物理碳黑經常用來與塑膠混合以改進其化學或物理性質。例如增強其抗紫外線特性,充做增強劑性質。例如增強其抗紫外線特性,充做增強劑以提高塑膠製品強度或做為體積填充物以提高塑膠製品強度或做為體積填充物
以左圖為例,除易揮發性有機以左圖為例,除易揮發性有機物及增量劑、外其餘皆是物及增量劑、外其餘皆是PolymerPolymer 及及 CarbonCarbon 其含量其含量分別約為分別約為 52﹪52﹪ 及及 29﹪29﹪ 可直可直接由接由 YY 軸中讀出軸中讀出
Polymer
Carbon
Volatiles
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Thermal-Thermal-5454
提供整套完整系統 具有完善的介面設計 -- 加熱管線與氣體樣品槽 具有專業的 TG-IR軟體 --TimeBase Software
TGA/FTIR/Interface System
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Thermal-Thermal-5555
TGA/FTIR SoftwareTGA/FTIR Software
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Thermal-Thermal-5656
TGA Weight loss vs.FTIR Spectrumweight vs Time
TGA/FTIR SoftwareTGA/FTIR Software
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Thermal-Thermal-5757
結論
Thank you for your attention !Thank you for your attention !
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