熱分析技術簡介 (dsc, tga & dma)

博精儀博精儀器器

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

[email protected]


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


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


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)


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


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


Thermal-Thermal-77

Amorphous vs. Crystalline?

Amorphous Amorphous ThermoplasticThermoplastic

Crystalline Crystalline PolymerPolymer


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


Thermal-Thermal-99

Thermosetting Polymer

UNCURED PARTIALLY CURED TOTALLY CURED


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 %


DSC TechniqueDSC TechniqueDifferential Scanning Differential Scanning

CalorimetryCalorimetry

DSC TechniqueDSC TechniqueDifferential Scanning Differential Scanning

CalorimetryCalorimetry



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 ?



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。



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



Polymer Transitions

HeatFlow

Temperature

Tg

StressRelief

OrderingProcess

Cold Crystallization

Curing

Tm

Degradation

Start upTransient



DSC Thermal Curve of PET

吸

熱

放

熱



DSC for curing studies

Detection of Tg Onset of cure Maximum rate of cure (peak maximum) End of cure Heat of cure



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



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


TGA TechniqueTGA TechniqueThermogravimetric AnalyzerThermogravimetric Analyzer

TGA TechniqueTGA TechniqueThermogravimetric AnalyzerThermogravimetric Analyzer



Thermal Analysis applications - TGA

Pyris 1 TGAPyris 1 TGA


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.



TGA Design Concept

懸吊式懸吊式水平式水平式上置式上置式



TGA Thermal Curves



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



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



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


TMA/DMA TechniqueTMA/DMA TechniqueMechanical AnalyzerMechanical Analyzer

TMA/DMA TechniqueTMA/DMA TechniqueMechanical AnalyzerMechanical Analyzer



Thermal Analysis applications – DMA/TMA

DMA 8000DMA 8000


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)



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。



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’



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 …



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…



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



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



So frequency can act like temperature

Frequency

E’

Temperature

E’



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



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



多樣化的夾具選擇

Options:

Single Cantilever

Dual Cantilever

3 Point Bending

Tension

Compression

Shear

Quartz Shear

Material Pocket



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



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



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



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



更多熱分析的應用更多熱分析的應用……


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



高分子的 Tg 分析 -- 加熱歷史的差異



結晶測試 -- 恆溫結晶



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:



交連測試交連測試 ---- 恆溫交連恆溫交連



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



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



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



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



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



TGA/FTIR SoftwareTGA/FTIR Software



TGA Weight loss vs.FTIR Spectrumweight vs Time

TGA/FTIR SoftwareTGA/FTIR Software



結論

Thank you for your attention !Thank you for your attention !

熱分析技術 簡介 (dsc, tga & dma)

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熱分析技術簡介 (dsc, tga & dma)