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熱分析技術 簡介 (DSC, TGA & DMA). PerkinElmer Thermal Specialist 康瑜容 Tiffany Kang [email protected] 常用的熱分析方法. Differential Scanning Calorimetry ( DSC ) Thermogravimetric Analysis ( TGA ) Thermomechanical Analysis ( TMA ) Dynamic Mechanical Analysis ( DMA ). 常用的熱分析方法. 高分子材料結構.

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slide1

熱分析技術 簡介

(DSC, TGA & DMA)

PerkinElmer Thermal Specialist

康瑜容 Tiffany Kang

[email protected]

slide2
常用的熱分析方法
  • Differential Scanning Calorimetry (DSC)
  • Thermogravimetric Analysis (TGA)
  • Thermomechanical Analysis (TMA)
  • Dynamic Mechanical Analysis (DMA)

Page 2

slide4
高分子材料結構

Type Structure Example

Type of Polymer Chain Structure

Poly(vinyl chloride), Polystyrene

Polypropylene

Polypropylene

Poly(imidazol pyrrolones)

Linear

Branched short chain

Long chain branching

Ladder

Page 4

slide5
高分子材料結構

Type Structure Example

Type of Polymer Chain Structure (Continued)

Phenol-formaldehyde resins

Two crosslinked polymers not bonded to each other

Crosslinked epoxy with vinyl polymer

Star

Network

Interpenetrating network (IPN)

Page 5

slide6

Polymers

Thermoplastics

Thermosets

(No chemical change on heating)

(Chemical change on heating)

Uncured

Cured

Amorphous

Crystalline

Polystryene

LOW/MEDIUM

HIGH

Epoxies

Rubber

Polycarbonate

Nylon

PPS

Polyimides

Silicones

Polyurethanes

PET

PP

Polyesters

Neoprene

Polysulfone

Acetal

HDPE

Phenolics

Epoxy

高分子材料的分類

Page 6

amorphous vs crystalline
Amorphous vs. Crystalline?

Amorphous Thermoplastic

Crystalline Polymer

Page 7

semi crystalline polymer
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

Semi-Crystalline Polymer

Semi-Crystalline Polymer

Page 8

schematic results in thermal analysis
Schematic Results in Thermal Analysis

Quality of sample process DSC(Ex) TGA TMA DMA

-Solid Melting

  • Crystalline
  • Semi-crystalline
  • -Amorphous
  • -Semi-crystalline
  • -General
  • -Liquid
  • -Unspecific

Recrystallization

Sublimation

Solid-solid transition

Glass transition

Softening without Tg

Post-crosslinking

Decomposition

Ligand release

Evaporation

Chemical reactions

Determination of %

Page 10

slide11

DSC Technique

Differential Scanning Calorimetry

question
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?

Page 12

what is dsc
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。

Page 13

thermal analysis applications dsc
Thermal Analysis applications - DSC

Diamond DSC

  • Principle:
  • Heat flow change vs. temperature
  • Measures:
  • Phase transition (Tg, Tm, Tc) and heat
  • Curing reaction and other chemical reactions

Page 14

polymer transitions

Tm

Stress

Relief

Cold

Crystallization

DH

Heat

Flow

Degradation

Tg

Start up

Transient

Curing

Ordering

Process

Temperature

Polymer Transitions

Page 15

dsc thermal curve of pet
DSC Thermal Curve of PET

吸 熱

放 熱

Page 16

dsc for curing studies
DSC for curing studies
  • Detection of Tg
  • Onset of cure
  • Maximum rate of cure (peak maximum)
  • End of cure
  • Heat of cure

Page 17

slide19
DSC的設計方式

熱流式 Heat Flux DSC

熱補償式 Power Compensation DSC

  • 直接量測DH
  • 不需複雜數學運算
  • 爐體較小
  • 量測DT
  • 由DH = kDT計算DH
  • 爐體較大

Page 19

slide20

TGA Technique

Thermogravimetric Analyzer

thermal analysis applications tga
Thermal Analysis applications - TGA

Pyris 1 TGA

  • Principle:
  • Weight change vs. temperature
  • Measures:
  • Compositions and wt%
  • Thermal stability and decomposition temp.

Page 21

tga design concept

懸吊式

水平式

上置式

TGA Design Concept

Page 22

slide24

TGA 的設計原理

主要元件

  • Temperature control device
  • - Furnace, Thermocouple
  • Weight measurement device
  • -Null Balance

Detector

Torque Motor

Sample

Tare Weight

Page 24

slide25
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熱重分析儀

Page 25

tga for compositional analysis
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

Page 26

slide27

TMA/DMA Technique

Mechanical Analyzer

thermal analysis applications dma tma
Thermal Analysis applications – DMA/TMA

DMA 8000

  • Principle:
  • Viscoelastic properties vs. temperature (DMA)
  • Dimensional change vs. temperature (TMA)
  • Measures:
  • Glass transition point
  • Storage, Loss modulus and tan delta
  • Coefficient of thermal expansion (CTE)

Page 29

what is dma
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。

Page 30

slide30

E”

E’

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 d = E” / E’

Page 31

slide31
什麼時候您需要 DMA …
  • 黏彈機械性質

ex. 模數(Modulus), 黏度(Viscosity), 阻尼相(tan d) …

  • 微小的相變化

ex. b,g- transition, Tg以DSC/TMA測量不易者 …

  • 活化能(ActivationEnergy)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 …

Page 32

slide32

 = 0

o

o

彈性

o

o

time

o

k

 = 90

time

黏性

time

o

o

time

材料的黏彈性質…

DMA即為利用Sine Wave震盪方式, 測量回應的分析儀

Page 33

idealized dma scan

For purely crystalline

materials, no Tg occurs.

Tg

(6)

Tb

Taor Tg

(5)

(4)

Tg is related to Molecular mass

up to a limiting value.

(3)

In semicrystalline polymers,

a crystal-crystal slip, Ta* occurs.

Beta transitions are often

related to the toughness.

E’/Pa

Rubbery Plateau (2)

For thermosets,

no Tm occurs.

Rubbery plateau is related to Me between crosslinks or entanglements.

Tll in some

amorphous

polymers

Tm - melting (1)

Temperature /K

  • (6) (5) (4) (3) (2) (1)
  • local bend side gradual large chain
  • motions and groups main scale slippage
      • stretch chain chain
Idealized DMA Scan

Page 34

frequency effects things too
Frequency effects things too
  • Transitions shift
  • Behavior changes

More

elastic

E’

More

fluid

Frequency

Page 35

so frequency can act like temperature
So frequency can act like temperature

E’

E’

Frequency

Temperature

Page 36

slide36

材料結構特性

成品特性

Molecular weight

MW Distribution

Chain Branching

Cross linking

Entanglements

Phases

Crystallinity

Free Volume

Localized motion

Relaxation Mechanisms

Dimensional Stability

Impact properties

Long term behavior

Environmental resistance

Temperature performance

Adhesion

Tack

Peel

Material

Behavior

製程加工特性

Stress

Strain

Temperature

Heat History

Frequency

Pressure

Heat set

DMA 連結...

Page 37

slide37
DMA 是如何運作的?

Total Force

Force motor

Static Force

Dynamic Force

LVDT

f

Frequency

Storage Modulus

Amplitude

K

Fixtures

Hold Sample

Position

Loss Modulus

d

Phase

Thermocouple

Furnace Options from -190 to 600 C

Page 38

slide38
多樣化的夾具選擇

Options:

Single Cantilever

Dual Cantilever

3 Point Bending

Tension

Compression

Shear

Quartz Shear

Material Pocket

Page 39

exclusive material pockets
Applications

Powders like drugs, excipients, foods, natural products, etc.

Gels

Uncured adhesives

Coatings

Samples that can’t support their own weight

Exclusive Material Pockets

Pocket closed & sealed

Sample in Pocket

Pocket open

Page 40

dma mode for mechanical properties change
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

Page 41

dma most sensitive indicator of cure
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

Page 42

tma mode for dimensional change
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

Page 43

slide47

交連測試 --升溫交連

Epoxy Resin

Endothermic

Range:

30 mw

Heating Rate:

20 oC/min

Weight:

32.76 mg

Run 1

62.8 oC

D

H

Heat Flow (mW)

113.3 oC

Run 2

40

80

120

160

200

240

280

T (oC)

Page 48

slide49

DSC Tg As

Function of Cure

DSC Heat Flow

Less

Cured

More

Cured

Temperature

交連測試 --交連度的影響

Page 50

slide50

More

Cured

Decrease in

Cure Exotherm

As Resin Cure

Less

Increases

Cured

Temperature

交連測試 --交連度的影響

DSC Heat Flow

Page 51

filler
填充物 Filler

填充物的功能

  • 降低熱膨脹係數
  • 增高熱導係數
  • 增加尺寸安定性
  • 降低成本
  • 改變密度
  • 改變黏度-方便加工
  • 降低吸水性

常用的填充物

  • 吸水性
  • 環氧樹脂
  • 二氧化矽
  • 碳黑
  • 玻璃纖維

Page 52

carbon

Polymer

Volatiles

Carbon

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

以左圖為例,除易揮發性有機物及增量劑、外其餘皆是Polymer及Carbon其含量分別約為52﹪及29﹪可直接由Y軸中讀出

Page 53

tga ftir interface system
TGA/FTIR/Interface System
  • 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

Page 54

slide55

TGA/FTIR Software

TGA Weight loss vs.FTIR Spectrum

weight vs Time

Page 56

slide56
結論

Thank you for your attention !

Page 57

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