長澤佳克 - vinalab.org.vn · separation (chromatographic), chemical analysis, ... physical...

1

2015/08/06

JAIMA Seminar in Ho Chi Minh City

長澤佳克

Yoshikatsu Nagasawa Ph.D

Instrumental Analysis Overview

and

Analysis of Food Packaging Materials

1

2

Change of the Subject in Japan201020052000

Resist material

Plating bath

Electronic paper

Fuel cell

Org-EL

Nano-hybrid materials

Biomedicine

Low-k、High-k

Li-battery Solar cell

MEMS

LED lighting

SiC

CNT，Fullerene

GaN:LEDGaAs

Exhaust gas catalysts

RO membrane

Dioxin

3D-MountingCMP

GHG

Lead-free solderSi deviceTextileFilmResin

Magnetic TapeHard DiskOptical Fiber

Biomass

Sensor

Generic Medicine Compound DrugsRegeneration medicine

Medical devicexxx: Electronics, Device

xxx: Energy, Environmentxxx: New materials

xxx: Life science Automotive

Packaging Materials, Packaging Film , Laminate Film, Nano-Laminated Film

3

Constitution of Advanced MaterialsMetal

SemiconductorInorganic materialOrganic material

(Polymer)

Organic material

Composite, Miniaturization, Laminating, Thinning, Integration (Thin layer, Fine particles, Additive)

•Materials forBuilding industry, Machine industry,Energy industry, Food industry, Textile Industry, Electronic industry・・

Electronic Device, Photoelectric conversion element, Functionality fiber, Cosmetics, Dispersing agent, Surfactant, Coating agent, Colors, Pigments, Laminated film, Catalyst ･･

Nanotechnology ! Nano particles, Nano layers

• High-performance materialsHigh strength, Super lightweight, High heat resistance, High electric conductive, Low resistance, High transparence, High response speed, Biodegradability, Biocompatibility, Environment-friendly

These products consist of various materials.

4

Constitution of Advanced MaterialsMetal

SemiconductorInorganic materialOrganic material

(Polymer)

Organic material

Composite, Miniaturization, Laminating, Thinning, Integration (Thin layer, Fine particles, Additive)

•Materials forBuilding industry, Machine industry,Energy industry, Food industry, Textile Industry, Electronic industry・・

Electronic Device, Photoelectric conversion element, Functionality fiber, Cosmetics, Dispersing agent, Surfactant, Coating agent, Colors, Pigments, Laminated film, Catalyst ･･

Nanotechnology ! Nano particles, Nano layers

• High-performance materialsHigh strength, Super lightweight, High heat resistance, High electric conductive, Low resistance, High transparence, High response speed, Biodegradability, Biocompatibility, Environment-friendly

These products consist of various materials.

You should Control an Atomic and a Molecular Level Chemical structure, Crystal structure & Morphology !

5

The study of the separation, identification, and quantification of the chemical components of

natural and artificial materials using chemical technique, spectrophotometric technique.

The Spread of Instrumental Analysis!

• Study of Qualitative & Quantitative analysisSeparation (chromatographic), Chemical analysis, Spectroscopic analysis

• Pursuit of the high reliability “Precision” “Accuracy”→ 「Quality control, Shipment management」*

• Development of a trace and an ultra trace level quantitative analysis (ppb)

→ 「Mercury, Dioxin, Semiconductor Impurities」*

*Analytical Chemistry in Industry

Analytical Chemistry in 20th Century

6

Challenge to ultimate analysis!

A fusion of chemical analysis and datamining technology!

• Measurements of ultralow concentrationDetection of one atom, one molecule. ppt, ppq, fmol, amol.

• Analysis of an atomic and a molecular level Matter Morphology, Composition, Chemical structure, Crystal structure

• Measurements of bioactivity, physiologic functions Comprehensive analysisGenomics, Proteomics, Analysis of gene expression,

High throughput screening

Analytical Chemistry in 21st century

7

Analytical Chemistry in 21st century

• In-situ analysis Inline Online analysis, Monitoring system

• Developments of hardware and software– Highly developed, Ultra-high sensitive instruments :

Large scale analysis facility (SOR etc.), Compact analytical device (MEMS utilization)

– Related advanced technologyRobotization, High selective separation technology, High selective or high sensitive detector, High brightness source

– Fusion with digital technologyLarge data transmission, Data mining, Image processing, Connection with LIMS, etc.

8

Comparison of 20th Century and 21st Century

J.Phys.Chem.,82, 1989(1978)

Cadmium Arachidate on Glass by FTIR-ATR Method

Barium Arachidate on Si. In Transmission mode

2 layers (5.59nm)2001

FTIRDuration: A Half Day Duration: 10min.

9

Evolution of Analytical Instrument in 21stC

Stability User-friendlyHigh-throughputHigh-sensitivity

High data-processing capacity↑

Contribution of Digital Technology and

Personal Computer

10

Role of Analytical Chemistry in Industry

• Qualitative & Quantitative analysis↓

• Clarify the Chemical State and Morphology

• Elucidate Chemical Structure

• Clarify Chemical and Physical Properties.

Development of Composite, Semiconductor, Nano-Material 「Material Characterization」Surface, Interfacial Analysis. Analysis of Crystal Structure, Molecular Orientation, Molecular Interaction.

Measurements of Ultralow ConcentrationDetection of Morphology, Composition, Chemical Structure, Crystal structure at an Atomic level or a Molecular level Matter

10

11

Material Characterization withAnalytical Chemistry

Molecular Structure :Component, Additives, Impurity, ElementsHPLC，ＧＣ，ＦＴＩＲ，NMR，GC-MS，LC-MS．MALDI-MS，ICP，IC，XRD，XRF

FTIR，RAMAN, SSNMR, GPC，XRD, DSC,Morphology: Crystallinity, Layer Construction, Phase-Seperation

SEM，TEM(STEM)，SPM，AEM，XRD, GD-OESPhysical Property: Thermal Property, Mehcnical Property, etc.

DSC，Viscoelasticity, Pore diameter

Molecular Structure: Molecular Weight, Crystal Structure,aaaaaaaaaOrientation

Design confirmation : Composition, Crystal Structure, Layer Structure

Troubleshooting： Alien Substance, Foreign Materials Change of Color, Break Away

Solve Degradation/Deterioration: Time Degradation, Thermal Degradation, Photo Degradation, Mechanical Deterioration

12

Analytical Chemistry in IndustryAnalysis of

Food Packaging Materials

13

Analytical TechnologyNecessary from R&D through Production

“Acceptance inspection”“Shipping inspection”

“Failure analysis”

“Degradation mechanism”

TreatmentSynthesisCleaningAssemblingMounting

Clean technologyHigh efficiencyQuality control

Bulk analysisStructure

ComponentTrace

Surface AnalysisInterface AnalysisMicroanalysis

Contamination

Foreign material

Process Development

“Molecular Design”

“Structure Design”

“Physicality Control”

“Interaction”“Patent

Application”

R&D

Production Sales

“Cost cut”“Quality control”“Environmental management”

“Ensuring safety”“Compliance ”“Complaints

handling”

14

Analytical Technology necessary from R&D through Production

“Acceptance inspection”“Shipping inspection”

“Failure analysis”

“Degradation mechanism”

TreatmentSynthesisCleaningAssemblingMounting

Clean technologyHigh efficiencyQuality control

Bulk analysisStructure

ComponentTrace

Surface AnalysisInterface AnalysisMicroanalysis

Contamination

Foreign material

Process Development

“Molecular Design”

“Structure Design”

“Physicality Control”

“Interaction”“Patent

Application”

R&D

“Cost cut”“Quality control”“Environmental management”

“Ensuring safety”“Compliance ”“Complaints

handling”

Production Sales

•Problem occurred in technology transfer from R&D to Manufacturing

•Post Marketing Complain occurred （Failure, Defectiveness）

15

Classification of Analytical Chemistryin Company

1)Production management • Quality control (Acceptance inspection, Shop floor control,

Shipping inspection, Environmental data measurement)to provide steady production, even quality.

• Process control (process monitoring, Inline Online analysis) for productivity maintenance, prevention of trouble.

2)R&D support works Structure design verification, Reaction confirmation, Application, Patent application, Reverse engineering, Complaints handling

3)Analysis based on regulations, laws and ordinances• Environmental analysis: Public regulation items such as soot particle,

the quality of the water, radiation measurement．

• CSR connection: Inspection examination proof, product proof,

material safety data sheet．

16

Classification of Analytical Chemistryin Company

1)Production management • Quality control (Acceptance inspection, Shop floor control,

Shipping inspection, Environmental data measurement)to provide steady production, even quality.

• Process control (process monitoring, Inline Online analysis) for productivity maintenance, prevention of trouble.

2)R&D support works Structure design verification, Reaction confirmation, Application, Patent application, Reverse engineering, Complaints handling

3)Analysis based on regulations, laws and ordinances• Environmental analysis: Public regulation items such as soot particle,

the quality of the water, radiation measurement．

• CSR connection: Inspection examination proof, product proof,

material safety data sheet．

Detection of Morphology, Composition, Chemical Structure, Crystal structure at an Atomic level or a Molecular level Matter

17

EDX and FTIR are widely used for analysis of foreign contaminant matter, but recently, these instruments are increasingly being utilized in tandem to conduct contaminant analysis1). While identification using any of these instruments and analytical methods independently is limited to some degree, using them in conjunction with one another permits a more detailed elucidation of the contaminant characteristics, thereby enhancing the validity of the respective results.

Contaminants Analysis in Food Manufacturing Process

-by EDX and FTIR

Application News No.X261 Shimadzu Corporation, 2015

18

Pretreatment and Analysis Procedure


19

Qualitative-Quantitative Result of Sample 1

Sample 1 Characteristics: Metallic luster, hard, silvery white


20

Qualitative-Quantitative Result of Sample 2

Sample 2 Characteristics: Metallic luster, hard, silver


21

Qualitative-Quantitative Result by EDX

Sample 3 Characteristics: No metallic luster, brittle, brownish red


22

80010001200140016001800200024002800320036004000cm-1

Abs

― Polyethylene― Oil/Fat― Polysaccharide― Sample3

Infrared Spectra and Search Result


23

Measurement Result Possible SourceTotal Findings

Found by EDX and FTIR

EDX

Detected 19K, 20Ca, and other food components.Principal component is 9F and below. (RhK�αC is Fig.2))

Food clumpPolyethylene with

attached food components

FTIRPolyethylene, oils and fats, polysaccharides

Polyethylene with attached oils/fats and polysaccharides

Analysis Results of Sample 3


24

Qualitative-Quantitative Results of by EDX

Sample 4 Characteristics: Non-metallic luster, hard, black


25

Infrared Spectra and Search Result of Sample 4

Analysis Results for Sample 4


26

Qualitative-Quantitative Results of by EDX

Sample 5 Characteristics: Some metallic luster, hard, black silver color

Regarding the EDX quantitative analysis results• Organic material is represented by CH2O, and was balanced.• Abundant, small quantity, etc. are relative reference values.

(In order to collectively set plating, film and deposits, etc.)Application News No.X261 Shimadzu Corporation, 2015

27

Infrared Spectra and Search Result of Sample 5

Analysis Results for Sample 5


28

Micro-Analysis (FTIR)

29

→ Cannot avoid the trouble by the Foreign Materials

Foreign Material!, Aliant !, Foreign Matter!

Foreign Material？

Necessary of Microanalysis

Grasp Circumstances of Foreign Material Occurring

Observe Shape Morphology

Information of Element

Information of Component

To solve the problem

Foreign material is defined as any material that does not originate from the material (Product) or grew in a Product, which is not

familiar with the main material and produces a trouble.

Emphasizing the light, thin, short and small

.

30

Inorganic Plate

Micro-sampling Method（FTIR）

Foreign Material

Limit of Sampling

Impossible for Sampling

～５μｍ（On solid Substrate）～１０μｍ（In Resin）

Liquid, Low viscosity, In Sticky Material

Optical Microscope x200）

FTIR Microscope

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1000 1500 2000 2000 3000

Wavenumbers (cm-1)

Ａｂｓ

(1)Around Foreign particle

(2)Normal Area

Difference Spectrum (1) –(2)

Never found Spectrum of Foreign Particle

ＩＲ

PP Film Cross Section

SampleSample

Direct MethodDirect

Method

Direct MethodDirect MethodPP film 30μm thickness

Direct Transmission Methods

１０μｍ

Foreign Particle

Foreign Particle

Foreign Particle in Polypropylene film

32

1000 1500 2000 2000 3000

Wavenumbers (cm-1)

Technique of Micro-Sampling

Ｓｔｅｐ３／Squash Foreign Material and Measure by Transmission Mode

Micro-Sampling with Infrared Transmission Microscope is effective to o

btain much information exactly.

ResultsResults

Ｓｔｅｐ２

Ｓｔｅｐ３

Ｇｅ板

Ｓｔｅｐ１／Leave PP on Foreign material and Open

吸収帯の歪

ＳｉＯｘ

Organics besides PP

１０μｍ

Ａｂｓ

Ｓｔｅｐ２／Pick Up Foreign Material and Measure by Transmission Mode

Ｇｅ板

Distortion of BandMicro-Sampling with Hands

１０μｍ

33

Trouble Shooting :Foreign Small Particle

10mm15m 20mmBase Film

Embedding Resign ca.5mm thick

拡大

SurfaceCross Section

Confirm Position Thickness

Direct Measurement

Micro-SamplingIsolation from Base Film

Resign Embedding・Cross Section Making

4000 3000 2000 1000

wavenumber (cm-1)4000 3000 2000 1000

wavenumber (cm-1)

《IR Spectrum》

PMMA

《Raman Spectrum》

PMMA

CHCH

C=O

C-O

CH

CHC=O

C-C

Black Particle :Fe2O3

Raman Spectrum

The TRC News No.116 (Mar. 2013)

34

Trouble Shooting : Contaminant on Surface

＜Quantitative Analysis by NMR Silicone Oil on PET＞

Internal Standard :I.S.

※1,1,2,2-Tetrabromoethane（TBE)

1H-NMRI.S.

（TBE)↓

×× ×

×：solvent

▼：PET oligomer

▼

▼

Si-CH3

↓

《1H-NMR Spectrum of Recovered Extract》

9 8 7 6 5 4 1 0 (ppm)

～～

Film

Vessel for Collect Extract

Sample Vessel

Extract

《Recovering Contaminant of Surface》：One-Side Extraction

～～

Silicone 5.4g

10cmΦ


1

Importance of Interface in Packaging Materials

Packaging films are majorly used to enhance the shelf life of the food products or consumer goods.

Packaging films also offers protection and quality to the products.

The requirements of barrier properties of packaging materials against environmental factors vary with food products and, the increased level of system miniaturization and integration requires the deposition of thin films which are highly uniform, homogenous, conformal, dense, and free from defects, cracks and pinholes.

2

Packaging Connections.HP

Plastic lamination films are big families. Every kind of film has its advantage which other plastic film may not have. So, combination with several of them will obtain all-in- one unique physical characters.

Being printed logo and pretty designs on the surface film will make the laminated films become much colorful, attractive and more valuable. Charming printing is one of the most important sales means to expand business anyway.

No matter how many layers there would be, the inner layer must be sealable by heat blades of bag -converting machine, the outer layer must be printable and the middle layer or layers must have main barrier functions according to design purpose of packaging.

Packaging Connections HP

Laminated Film

http://www.beeradvocate.com/

3

Analysis of Gas in a Tablet Package

Storage Condition : ①Room Temperature (25±3 ℃）, Normal Humidity(60％）②High Temperature (80℃）, High Humidity(100％）, 20Hrs

Outer Packaging : Pillow-TypeMaterial : PE,PETVolume: ca 100mL

Inner Packaging : PTPMaterial : PVC, M(Al Foil)Volume: ca 0.5mL/1pocket

HPLC Derivatization TPD-MS

RT,NH

HT,HH

RT,NHHT,HH

Sealing in Air CO2 to N2 Ratio Increased

Aldehyde compound 1-10C

Conc. (ng/mL)Component

TRC Poster Session 2014

4

Analysis of Gas in a Tablet Package

GC/MS

Aldehyde of the C6 from C1

RT,NH

HT,HH

RT,NH

HT,HH

Aldehyde, Ketone and Toluene Increased

Organic Gases were generated from the package by heating in humid environment.

Outer Packaging : Pillow-Type

GC/MS

Inner Packaging : PTP

Conc. (ng/mL)

Component

ComponentConc. (ng/mL)


5

Importance of Surface & Interface

1. Role of Surface propertyWettability, Adhesiveness, Stickiness, Frictionality, Lubricity, Chemical Reactivity, Charging Property

2. Change, Degradation, Deterioration of SurfaceOxidation, Photo Deterioration, Chemical Deterioration, Bread Out of Additive and Oligomer

3. Surface Treatment, AlternationCoating, Graft Polymerization, Ion Implantation,Acid Treatment, Corona Discharge, Plasma Processing,UV Irradiation

6

Adhesion Mechanisms at InterfaceA Various Theory of Adhesion Mechanism: Diffusion, Lifshitz-van

der Waals interactions, Molecular interactions, Mechanicalinterlock, Chemical bonding, Electrostatic

The strength of the adhesion between two materials depends on which of the above mechanisms occur between the two materials, and the surface area over which the two materials contact. Adhesion level also depends on the substrate materials and process temperature and Humidity

Poor Adhesion, Peeling Defects ←Inhibiting Adhesion Factors

Physical Bonding

Dispersive, Non-DispersiveForces (Polar, HydrogenBond…)

+ - + -+ - +-

Mechanical Interlock

Adhesive flowing into pores and get physically stuck upon polymerizing.

Chemical Bonding

Formation of chemical bonds between adhesive and adherent

C

B

A

C

B

A

C

B

A

C

B

A

Diffusion

Adhesive Weaving into Adherent or Both Polymers Cross Interface.


7

Cause of Poor Adhesion, Peeling Defects

Poor Adhesion, Peeling Defects have Several Patters

Destruction in Layer

Check the Pattern in Morphological Observation

Peeling at Interface

Exists Inhibiting Factor between Interface

Destruction in Adhesive

Exists Inhibiting Factor in Adhesive

Destruction in Adherent

Exists Inhibiting Factor in Adherent

adhesive

substrate


In the issue of peeling , we have to identify the peeling surface.→ FTIR-ATR, XPS, SEM-EDX

8

FTIR-ATR Spectra of Peeling Surface

ATR spectrumof Peeling Surface

ATR Spectrum of Base Film

1000150020002500300035004000

abso

rban

ceab

sorb

ance

1000150020002500300035004000

Difference Spectrum

1000150020002500300035004000

abso

rban

ce

Silicone

9

Causative agent of Poor Adhesion, Peeling Defects

→ Surface Contaminant, Bleed Out,Existence of Foreign Material

• Contaminant from Air

• Residue of Release Agent

• Residual Monomer and Oligomer from Resin.• Void Jammed by Air or Degas from Resin.

• Lack of Surface Treatment (Washing, Corona

Processing, Plasma Processing)

Analysis ： TOF-SIMS, XPS, FT-IR, Micro-IR, Contact Angle, SEM, TEM [Detection of Contaminant, Foreign Material.]



Exists Inhibiting Factor between Interface

adhesive

substrate


10

Causative agent of Poor Adhesion, Peeling Defects

→ Deterioration of Polymer

• The Polymer is easy to be hydrolyzed?

• Contacts with Reactive Metal?

• How about environment? (Heat, Ultraviolet Rays, Oxygen, Ozone, Water, Acids, Existence of the alkali)

• Excessive Surface Treatment? （Excessive Washing,

Corona, Processing, Plasma Processing made Brittle

Surface Layer.)

Analysis to Identify Deterioration：FT-IR, NMR, XPS, GPC, TPD-MS, SEM,TEM

Destruction of PolymerDestruction

in Layer

Lack of Polymerization or Excessive Reaction ⇒ made Brittle Layer


11

Factors Influence adhesive property and Analytical Techniques

Factors influence Adhesive Property Analytical Technique Potentials

Wetability, Surface Free EnergyContact Angle (Caluculation ofSurface Free Energy）

Establishing Adherent ModelRelation with Adhesive Strength

GD-OES High Sensitivity, Rapid Depth Profile

XPS （with Chemical Modification)High Surface Sensitivity, GoodQuantitativity

TOF-SIMS (GCIB Sputtering)High Surface Sensitivity,High Spacial Resolution,High Detection Limit

FT-IRA lot of Structure InformationMolecular Orientation

Surface Fine Structure SEM EDXObserve Highly Sensitively SurfaceShape, Easy to Use

Interface Ultra Fine Structure TEM EDXObserve nm order InterfaceStructure

Anchoring Effect, (Increase Surface Area) AFM Quantification of Surface Roughness

Mechanical & Thermal Property of Surface VE-AFMHigh Spacial Resolution,Semi-Quantification

Nano IndentationEvaluate Hardness and Elastisity ofnumber of the outer layers 10nm,

μTA, Fast-DSC Tg, Mp of Small Area, Small Sample（VE-AFM：Visco-Elasticity Atomic Force Microscopy）

Cohesion of Adherend, Stress Concentrationin Peering

Composition, Chemical Structure, FunctionalGroup of Surface

(Chemical Bond, Intermolecular Force)


12

Corona Discharge Treating on PETCorona Discharge Treatment for Bonding Easily

Contact Angle and Surface Free EnergyContact Angle of Probe Liquids

0 20 40 60

After

Before

Surface Free Energy （mN/m）

Dispersion Component

Polar Component Hydrogen Bond Component

Droplet Shape of Ethylene Glycol

Before

After

Gas Phase Chemical Modification for XPS Trifluoro-acetic Acid modification

Surface microscopic observation by AFM

Surface Roughness

Before After

AFM Image（400 nm□）

O/C -COH/C -COOH/C

Before 0.40 0.004 0.003

After 0.45 0.023 0.017

Atomic Ratio and Amount of Functional Group Ra Rms Rmax 表面積超過

Before 0.65 nm 0.81 nm 5.9 nm 0.58 ％

After 0.95 nm 1.24 nm 9.2 nm 1.13 ％

Before 65.5゜ 48.3゜ 37.7゜ 22.3゜

After 54.0゜ 29.9゜ 15.9゜ 26.4゜

WaterFormamideHCONH2

Ethylene Glycol(CH2)2(OH)2

Methylene iodideCH2I2

LiquidSample

Before

After


13

GD-OES ： Pulsed RF Glow Discharge Spectrometry

RF Electric Power

Ar+

Sputtering

Excitation

Emission

Emission Spectrum Analysis

• Measurement of Emission from Excited Species in Ar Plasma.• Rapid Spattering enable to investigate to more than 150 microns depth with as

good as 1 nm depth resolution.

Sample

.

Pulsed RF GD-OES is the only technique that can provide both surface, depth profile and bulk composition, and with high sensitivity to all elements for almost all solid materials, including metals, metal alloy coatings, glass, semiconductors, polymer coatings, etc.It relies on the controlled sputtering of a representative area of the material of interest and the simultaneous detection of the sputtered species. Pulsed RF GDOES is the ideal tool to investigate from the surface down to more than 150 microns with a depth resolution that can.


HORIBA Ltd. HP

14

GD-OES Results of Laminated Packaging film

Laminated Film Non-chlorine-based Film

Depth Depth

Cl : Originated from PVDC High Si Concentration at

Surface

Nor

mal

ized

In

ten

sity

Nor

mal

ized

In

ten

sity


15

What is the Gas Cluster Ion Beam?The Gas Cluster Ion Beam (GCIB) technology is an advanced technology from Japan,

developed at Kyoto University. GCIB is an ion beam consisting of several thousand gas atoms (molecules) such as argon, which enables ion beam etching with extremely low energy per atom and surface flattening after etching, not possible with other ion beam technologies.

Comparison of the characteristics of ion beams of the past and cluster ion beams

ULVAC-PHI, INCORPORATED HP

16

What is the Gas Cluster Ion Beam?In surface analyses such as XPS and TOF-SIMS, cluster ions have always been used. Among

cluster ions, C60 ions in particular are capable of surface cleaning and low damage sputter etching on many polymers and organic materials, and are thus used in many commercial analyzers, with several dozen currently in practical use for surface analysis around the world. Ar gas cluster ion beams leave hardly any recognizable chemical change caused by the irradiation ion on the post-etching surface, it enables low damage/high depth resolution etching with ultra-low energy ion etching at approximately 1 to 20 eV per atom, which cannot be accomplished with C60.

Overview of gas cluster ion beam instrument

ULVAC-PHI, INCORPORATED HP

Overview of gas cluster ion beam instrument

17

GCIB/TOF-SIMS Analysis of Laminated Polymer film

GCIB enables the depth profile of Laminate Film!

18

Al/Polymer Interface AnalysisGCIB-TOF-SIMS Analysis

PET/PE①/Al/PE②/LLDPE Primary Ion :Bi3+, Etching Ion :Ar +Cluster

From Front Surface (PET Film)

From Back Surface (LLDPE Film)

New Thin-Film Preparation

In GC=IB, Etching Rate of Metal is very slow!

Long Etching Time and Existence of Inorganic Filler Roughen Measurement Surface.

New Thin-Film Preparation Technique Altars Depth

Resolution about Fifty Times

Existence of PET Oligomer, PDMS and Mg at Al/PE

Interface.Preparation

Analysis


19

Before and After One Side Elution TestGCIB-TOF-SIMs Result after Elution Test of Food Packaging Material

One Side Elution Test : 50% EtOH, 110℃, 10hrs

Before After

CNO :Origin of Nylon

Cl :Origin of PVC

Surfactant

CNO :Origin of Nylon

Cl :Origin of PVC

Surfactant

AntioxidantAntioxidant

UV AbsorberUV Absorber

Cl and Surfactant Distributions Varying!

Surfactant near Interface Spread into Nylon Layer and Phosphorus-based Antioxidant-assistant also Spreads into Nylon Side.


Elution Penetration

SolventJig

Food side layer

Functional layerLaminate film

Outer layer

1

SEM Image of Al Evaporated PP filmFiller

Evaporated Al

Evaporated Al 50nm

Ink

Polypropylene

SAMPLE PREPARATION BY MICROTOME

SAMPLE PREPARATION BY ION POLISHING

Enlargement Enlargement

Nitto Analytical Techno-Center Co HP

22

FIB-SEM RESULTS （Cross Section of Wrapper ）Overall Image of

Cross sectionFIB Image

Backscattered Electron Composition image (BEC)

SEM Image (SEI)

Enlargement

33

FIB-SEM RESULTS （Cross Section of Wrapper ）

Ti Particle Layer

Organic Layer (C,O etc.)

Al Layer

Presented by JEOL Ltd.

4

TEM Image of Metallic Luster Forming Film

Co-Polymerization PET

TORAY Advanced Material Symposium 2006TORAY HP

Metallic Luster Forming FilmAn entirely new film with metallic luster without using metal

Items: Environment-friendliness, light transmittance, electromagnetic wave transmission, formability

Focus: To develop a film with superior properties of environment-friendliness, light transmittance, electromagnetic wave transmission and formability by not using metal

Impacts: We were able to achieve metallic luster and light transmittance with innovation of film structure alone. The film can replace plating, coating and metal vapor deposition

5

Method, Instrument

Wave Length Nature Spatial

Resolution Information

Micro-FTIR 10μm Molecular Vibration

～１０μm Functional Group, Orientation,

Crystallinity Molecular Interraction

RAMAN Microprobe

1μm Molecular Vibration

～１μm Skeleton Structure, Orientation,

Crystallinity

UV-VIS Microscope

300nm Electronic Transition

～１μm Electric Structure

XPS 10nm Electronic Transition

１０μm Surface Element, Functional Group

TOF-SIMS 100eV Ion Mass 200 nm Chemical Element, Chemical Structure,

Mapping

TEM･SEM-EDX 100keV Electric State （XRF）

0.1nm Chemical Element, Element Mapping

TEM-EELS 100keV Elastic Scattering Core Excitation

0.1nm Chemical Element, Mapping

Instruments for Micro-Analysis

6

Instruments for Surface AnalysisMethod

InstrumentProbe Detect signal

Application Implementation

DepthResolution

Detection Limit

SpatialResolution

XPS（ESCA） X-ray Photo ElectronElement Chemical

Shift, Map2～5 nm ％ 10 µm

TOF-SIMS Ion Second. IonElement, Chemical

bond, Map1～2 nm ppm 200 nm

EPMA Electron Beam X-ray Element, Map 1 µm ％ 1 µm

SEMSurface

Morphology1 µm ％ 0.7 nm

TEM, STEM, Electron Beam Electron Morphology, 0.1 nm 0.1 nm 0.1 nm

SPM Needle Atomic force etc.Surface

Morphology, Roughness

0.1～nm 0.01 nm 0.1 nm

Laser RAMAN Visible Ray Raman scattering

Chemical bond,Orientation、Crystallinity, Identification

10 nm ％ 0.5 µm

FTIR Infrared RayTransmissionReflection Ray

Chemical bond,Orientation、

Second. Structure,, Identification

100 nm ％ 8 µm

7

Devices for Preparation

Bulk Analysis• Microwave Digestion

• Ultra-centrifugal Separator

• Preparative HPLC

Surface Analysis, Micro-Analysis• Cutting Machine: Microtome, Diagonal Cutting

• Etching Device ; Dry Etching, Reactive Ion Etching, Ion milling, Ion polishing, FIB(Focused Ion Beam)

• Hybrid Techniques; FIB-SEM, IP-SEM, SIMS

Inorganic, Organic Analysis

8

まとめSummery of Analysis Procedure

8

Observation of Peeling Area


Destruction in Layer

Contaminant, Foreign Material

１．Deterioration of Resin

２．Interface Destruction, Cohesive Failure

TOF-SIMS, XPS, FTIR, Micro-IR, Contact Angle, SEM etc.

TEM, SEM, TOF-SIMS, FT-IR etc.

FTIR, NMR, XPS, GPC, TPD-MS etc.

FTIR, RAMAN, DSC, XRD, KF method, TPD-MS, GC,Linear Expansion Coefficient, Polarizing Microscope etc.

1

Appendix

2

Features of EDX, FTIR

EDX-7000

IRTracer-100+AIM-8800


3

Analytical Conditions ［EDX］

Instrument : EDX-7000

Elements : Na-U

Analytical Group : Qualitative-quantitative

Detector : SDD

X-ray Tube : Rh target

Tube Voltage [kV] : 15,50

Current [μA] : Auto

Collimator [mmφ] : 1

Primary Filter : #2

Atmosphere : Vacuum

Integration Time [sec] : 50 /ch（3ch)

Analytical Conditions ［FTIR］

Instruments : IRTracer-100,AIM-8800Resolution : 8cm-1

Accumulation : 40Apodization : Sqr-TriangleDetector : MCTMode : Microscope

with ATR Attachment

Analytical Instruments and Analytical Conditions


4

Raman Spectrometer

4

Sample

Spectrometer

Grating

CCD detector

Data processor

Notch filter

5

IR Microscope

Cass grain type lens Objective lens & CCD camera

Infrared semitransparent mirror

Aperture, Mask

Cass grain type lens

Stage & Sample

Cass grain type lens

Infrared semitransparent mirror

(Aperture, Mask)

Visible light

MCT detector

Infrared ray

6

Attenuated Total Reflection(ATR)

Incident Angle : θWave Length : λ

Sample

n1

n2

Refractive Index :nn1＞ n2

θ

ATR Crystal

dp ：Penetration Depth

Multiple Reflections

θ

Ge=4.0

Metal Plate

Diamond ATR

CrystalSample

IR ray Supporting Element

Single Reflection Attachment

Shimadzu Cooperation. HP

7

Cross Section Polisher

図1-1 CPの模式図図1-2 加工時の模式図

Ar Ion Gun

Masking Plate

Specimen

Masking Plate

Specimen

Principle of CP Principle of CP with a Masking Plate

Cross Section

Jeol HP

The CP uses an argon beam to mill cross sections or polish virtually any material that is affixed to the continuously rotating sample holder. There is no precedent for a cross sectioning instrument of this type for SEM, EPMA, and SAM sample preparation.

8

Surface Analysis

Electron Beam

Backscatteredelectron

X-ray

ION

Backscattered ion

X-ray

Photon X-ray

Photon

Auger electron

PhotonX-ray

Secondary electron :SEM

Auger Electron :AESX-ray :EDX,EPMA

X-ray :XPS（ESCA)Photon :FTIR, RAMAN

Secondary ion：SIMS

TOF-SIMSBackscattered ion

：RBS

Secondary electron

Auger electron

Secondary electron

長澤佳克 - vinalab.org.vn · separation (chromatographic), chemical analysis, ... physical...

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