MTT 552 Polymer Characterization and analysis point... · - Demonstration on the characterization...

MTT 656 Polymer Characterization and analysis

Assoc.Prof. Dr. Jatuphorn Wootthikanokkhan

Division of Materials Technology, School of Energy Environment and Materials, King Mongkut’s University of Technology Thonburi, Thailand

lnstructors

• Assoc. Prof. Dr. Jatuphorn Wootthikanokkhan (62.5 %)

• Dr. Nandh Thavarungul (18.75 %)

• Prof. Dr. Narongrit Sombatsompop (6.25 %)

• Dr. Sirinthorn Thongsang (6.25 %)

• Asst. Prof. Dr Sombat Thanawan (6.25 %)

Weeks Date Instructor Contents 1 14/08/2012 JWN Guideline for an identification of unknown polymer using simple

techniques. Physical and mechanical properties testing (specific gravity, hardness, impact resistance test, tensile test, adhesion test.

2 21/08/2012 JWN Fundamental of polymer molecular weight analysis techniques ;

Osmometry, Viscometry, End group analysis technique, Light scattering technique, Size exclusion technique (GPC)

3 To be confirmed

JWN Demonstration of the GPC technique at the Department of Chemistry, KMUTT

4 28/08/2012 JWN - Polymer spectroscopy (I): Fundamental of FTIR, ATR, and Raman

- Demonstration on the characterization of polymer chemical structure by using ATR-FTIR (internal reflection technique)

5 04/09/2012 STG Demonstrations on the tensile test, impact test and hardness test of plastics (at the Faculty of Engineering)

6 11/09/2012 JWN Polymer spectroscopy (II)

- Principle of NMR technique.

Cases study; quantitative analysis using FTIR, Determination of copolymer composition, Determination of MW from NMR.

7 18/09/2012 JWN Polymer microscopy (I): Fundamental concept and practical aspects of SEM, TEM

8 To be

confirmed

(tentatively Wednesday or

Thursday)

JWN Demonstration on SEM for polymers analysis (at the Faculty of Engineering)

Midterm Examination (25/09/2012)

Weeks Date Instructor Contents 9 02/10/2012 JWN & STW Polymer microscopy (II)

- Introduction to Atomic Force Microscopy AFM - AFM Instrument and applications in polymer microscopic analysis

10 09/10/2012 JWN & STW Polymer microscopy (III)

- Demonstration on the use of AFM technique at Mahidol University

(Salaya Campus) Case studies (using real polymer samples from KMUTT research work)

11 06/11/2012 NSP Measurement of flow properties of polymers

12 13/11/2012 NTL Thermal analysis techniques; DSC, DTA, TGA, DMTA, TMA

13 20/11/2012 NTL Demonstration on thermal analysis techniques

14 27/11/2012 NTL Optical microscopy technique (OM), X-ray techniques; XPS, XRD

15 04/12/2012 JWN Student presentations on polymer analysis

16 11/12/2012 JWN Student presentations on polymer analysis

Final Examination (18/12/2012)

แนวทางการน าเสนอ กลมท โจทย ตวอยาง

1 Polymer characterization and analysis

ถาจะวเคราะหพอลเมอรในโจทยดานใดดานหนง จะใชเทคนคอะไรไดบาง (มากกวา 1 เทคนค)

•Intercalation and exfoliation in polymer NANOcomposites •Determination of degree of crystallinity • Composition in blends, compounds and composites •Graft copolymer formation •Polymer-polymer miscibility

2 Applications of one selected technique เลอกมา 1 เทคนคแลวน าเสนอวา เทคนคดงกลาว ใชประโยชนในการวเคราะหพอลเมอรในดานใด ไดบาง (มากกวา 1 applications)

3 Recent progress in polymer characterization techniques น าเสนอความกาวหนา หรอพฒนาการในการวเคราะหพอลเมอร

(อาจจะเปนไดทง เทคนคใหมหรอเทคนคทเรยนแลว แตมการตอยอดพฒนาการใชงานและวเคราะห)

Discuss the papers in terms of sample preparation, limitation, advantages of each technique. Don’t have to present principle and concept of techniques which have been studied (but should be able to explain when asked).

แนวทางการน าเสนอ

• 20 min. (15 + 5 min), Do not prepare too many slides (โปรดรกษาเวลา) • Be careful about the citation (reference), and clarity of your power point

presentation (avoid copy and paste) (ระวงเรองการอางอง และความชดของรปและตาราง)

• Prepare to handle some question carefully (อยาประหมา ตอบใหตรงค าถาม) • Pay attention to your friend’s presentations. Make some contributions (ฟง

และมสวนรวมกบเพอนดวย) • Report (include corrections after obtaining some comments from the

presentation) Submit within 1 week after the presentation • ล าดบการน าเสนอ ???

Textbooks & References

1. Modern methods of Polymer Characterization, edited by H.G.Barth,and J.W.Mays,

John Wiley & Sons, New York, 1991

2. Spectroscopy of Polymers, 2 nd edition, edited by J.L. Konig, Elsevier, Amsterdam,

1999.

3. NMR of Polymers, edited by F.A.Bovey and P.A. Mirau, Academic Press, New York,

1996

4. Infrared Spectroscopy of Polymer Blends, Composites and Surfaces, edited by A.

Garton, Hanser Pubsishers, Germany, 1992

5. Polymer Microscopy, edited by L.C. Sawyer and D.T. Grubb, Chapman & Hall, New

York, 1987.

6. Handbook of Plastics Testing Technology, V. Shah, John Wiley & Sons, New York,

1984.

7. Polymer Surface Modification and Characterization, edited by C.M. Chan,

Hanser/Gardner Publishers, New York, 1994.

Measurements:

Lecturer / Measurement Midterm

examination

Final

examination

Presentation

and report

Total

Assoc. Prof. Dr. J. Woothikanokkhan 40 % 15 % 20 % 75 %

Dr. Nandh Thavarungul - 20 % - 20 %

Prof. Dr. N. Sombatsompop - 5 % - 5 %

Total 40 % 40 % 20 % 100 %

Mechanical behaviors of polymers

Mechanical tests of polymers

09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT

Tensile Test: Standard Testing Methods

– ASTM D638 , ISO 527 (tensile test of plastics) – ASTM D412 , JIS K-6301 (tensile test of vulcanized rubbers) – ASTM D 882-95A (tensile test of thin plastic sheeting)


Tensile Specimen

Lo

Thickness

Width

Cross-sectional area (m2) = Width x Thickness

Specimen preparations

• Injection molding (for thermoplastics)

• Compression molding (for both plastics

and rubbers) + dog-bone cutting die

• Film casting (for soluble polymers with

some limited amount) dog-bone cutting die

http://www.testresources.net/images/stories/jreviews/D412-dogbone-rubber-sample-cutting-die.jpg

Clip VDO tensile test of PVC sheet


Conversion to Stress-Strain

• Stress (N/m2 or Pa) = Force / Cross-sectional Area

• Strain (dimensionless) = Displacement / Initial length = L/Lo


Results from stress-strain curve

• Tensile strength at Break (MPa)

• Ultimate Tensile stress (MPa)

• Elongation (%) • Modulus (MPa) • Toughness (Nm)


Results from stress-strain curve

Typical stress-strain curves for samples exhibiting brittle

failure, ductile failure, ductile failure with cold drawing and hardening, and rubber with strain induced crystallization

Example of report from creep test

Characteristic features of stress-strain curve as related to polymer properties

Description of polymers

Modulus Yield stress

Ultimate strength

Elongation at break

Soft & weak Low Low Low moderate

Soft & tough Low Low High High

Hard & brittle High None Moderate Low

Hard & tough High High High High

From Billmayer, Textbook of Polymer Science , John Wiley & Sons


Examples

• Brittle plastics - Polystyrene, PMMA, unplasticized PVC • Tough plastic - Nylon, Polycarbonate (PC) • Soft plastic (or polymer) - plasticized PVC, and Rubbers • Hard and Strong plastic - Kevlar


Izod Impact Strength of Some Plastics

Polymers Impact Strength (J/m)Polystyrene 16-24HIPS 48-100ABS 100-450Poly(vinyl chloride) 50Rubber-toughened PVC 800Nylon 6,6 240Super Tough Nylon 1100-1200PMMA 16PMMA/Rubber 80

Data from “Polymeric Multicomponent Materials”,edited by L.H.Sperling, John Wiley & Sons, Inc. 1997

There are three main methods of testing 1. Charpy Impact Test 2. Izod Impact Test 3. Falling Weight Test (Dart

Test)


Impact test Izod impact strength = (E1-E2)/thickness

Standard test methods include

•ASTMD256; •BS2782 (method 306A) •ISO R180


Impact test

Charpy test

Izod test


Calculation of Impact Strength

• Impact strength (J/m) = Energy (J) / Specimen thickness (m)

ALTERNATIVELY • Impact strength

= Energy (J) / Area at notch section (m2) L

w

t


Sources of error in impact test

Impact strength depends on many factors including • Thickness • Notch size (radius) • Testing temperature • The presence of defect (stress concentrator)

These factors needed to be controlled (eliminated or specified in the report)


Falling weight test

Falling weight impact strength = (W)(H)

Standard test method include BS 2782 method 306B

Clip VDO on falling weight impact test


Calculation of Impact Energy

Failure energy (J) = hwf

where h = height (mm or inch) w = weight (kg or lb) f = factor for conversion to Joules


140 C

0

500

1000

1500

2000

2500

0 0.01 0.02 0.03 0.04Displacement (m)

Forc

e (N

)

100 % PVC

90/10

95/5

80/2070/30

60/40

PVC/Acrylic rubber blend at various compositions


PVC/AR Blends

Table 1. Effect of rubber content on mechanical properties of PVC-AR blends.

PVC/AR (% w/w) UTS (MPa) Modulus (MPa) Toughness (Nm)

100/0 53.0 37.2 10.7

95/5 51.6 33.9 13.1

90/10 47.1 28.5 16.2

80/20 24.6 16.7 18.8

70/30 14.8 7.4 13.5

60/40 8.5 4.4 10.6

Adhesion test

• 90 degree peel test

• 180 degree peel test

• Floating roller peel test

• T-peel test

• Lap shear test

90 degree peel test

90 degree peel test:

Peeling behaviors

Peel test Peel strength (N/m) = Force/strip width

Failure mode is also important

• Cohesive failure • Adhesive failure

Floating roller peel test ASTM D 3167

Determination of adhesion between EVA and glass substrate by 180 degree peeling test

http://www.photon-magazine.com/news/news_2005-04 ww feat PVB foils.htm

Case study : Development of curing

machine sleeve from EPDM sheet

T-peel test

Clip VDO T-Peel Test

Lap shear test

Hardness test • Hardness = resistance of a material to deformation. It is different to abrasion and

wear resistance. PS has a high hardness but low abrasive resistance. Hardness is also

not equivalent to modulus.

• Hardness test can be classified into several types including

– Rockwell hardness (ASTM D785, suitable for PS, PMMA, Nylon etc.)

– Durometer hardness (ASTM D2240, suitable for rubber, plasticized PVC, PE etc.)

Choice of Hardness Test Methods

Based on Modulus Range of Plastics

Materials Test method

Low modulus

Rubber Shore A

Plasticized PVC Shore A

LDPE Shore D

HDPE Shore D

Polypropylene Rockwell R

Toughened polystyrene

Rockwell R

ABS Rockwell R

Polystyrene Rockwell M

PMMA Rockwell M

High Modulus

Scale Major load (kg)

Diameter

of

indentor (in.)

R 60 ½

L 60 ¼

M 100 ¼

E 100 1/8

Rockwell hardness scale

Rockwell hardness test

Density and specific gravity

• Specific gravity = Ratio of weight of a given volume of materials

at 23 °C to that of an equal volume of water at the same

temperature

• Density = Weight per unit volume of material at 23 °C (g/ml)

Test of specific gravity

• Method A; A piece of the specimen is held by a wire, weighed and

submerged in water.

While it is in the water, the specimen is weight again.

From the weight difference, the density can be calculated

• Method B; This method, suitable for pellets or powder, requires the use of

an analytical balance, a pycnometer, a vacuum pump, and a vacuum descicator.

Test of specific gravity; Method A

This method requires the use of a

precision balance equipped with a

stationary support for an immersion

vessel below the balance pan.

A corrosion resistant wire for

suspending the specimen and a

sinker for lighter specimens are

employed.

1. The specimen is weighed in air (a)

2. The specimen is suspended from the

wire attached to the balance and

immersed completely in distilled

water. The weight of a specimen in

water (and a sinker if used) is

determined. (b)

3. The weight of totally immersed sinker

(if used) and partially immersed wire

is determined (w).

Specific gravity = a/ (a + w) - b

การหาคาความหนาแนน ของเมดพลาสตก

1. ชงน ำหนก ตวอยำงเมดพลำสตก ในอำกำศ (a)

2. จมตวอยำง ทแขวนกบลวดซงตออยกบเครองชง ลงในอำงน ำกลน

3. ชงน ำหนกตวอยำงดงกลำวในน ำ (อำจจะมตวถวงดวย) (b)

4. ชงน ำหนกตวถวงและลวด ในน ำ (w).

Specific gravity = a/ (a + w) - b

Test of specific gravity; Method B

1. Weighing the empty pycnometer.

2. The pycnometer is filled with water and placed in a water bath until temperature equilibrium with the bath is attained. The weight of the pycnometer filled with water (b) is determined.

3. After cleaning and drying the pycnometer, 1-5 g of material is added and the weight of the specimen plus the pycnometer is determined. From this, weight of the specimen can be calculated (a).

4. The pycnometer is filled with water and placed in a vacuum descicator. The vacuum is applied until all the air has been removed from between the particle of the specimen.

5. Lastly, the weight of the pycnometer filled with water and specimen is recorded (m)

Specific gravity = a/(b + a – m)

การหาคาความหนาแนนโดยใชคอลมมเกรเดยนท Determination of density by gradient test

• เตรยมจำกของเหลวทปรบควำมหนำแนนได เชน น ำ + แอลกอฮอล (ส ำหรบทดสอบพอลโอเลฟนส)

• ทระยะควำมสงตำงๆ ของคอลมม จะมสดสวนผสมของเหลวตำงกน • ของเหลวตอนลำงจะมสดสวนน ำสง ตอนบนมสดสวนแอลกอฮอลสง • หยอนลกแกวททรำบควำมหนำแนน ตำงๆ ลงไป ลกแกวจะอยทระดบ

ควำมสงทควำมหนำแนนตรงกบของเหลว • พลอตกรำฟมำตรฐำน ระหวำงระยะควำมสง กบควำมหนำแนนของลก

ลอยแกว • หยอนเมดพลำสตก สำรตวอยำงลงไป วดระดบควำมสง

Determination of density by gradient test

• The test is based on observing the level to which

a test specimen sinks in a liquid column

exhibiting a density gradient in comparison with

standard specimens of known density (glass

float).

• A number of calibrated glass floats of precisely

known density are introduced into the density

gradient and allowed to sink in the column to a

point where the glass floats’ density matches

that of the solution.

• The float position versus float density is plotted on a chart to obtain a calibration curve.

Tests for softening and deflection (distortion) temperatures of plastics

Vicat softening point is the

temperature at which the

needle penetrates 1 mm

into the sample.

Standard test methods include ASTM D1525, BS

2782 method 102D, ISO R306.

Vicat softening temperature test

Heat deflection temperature test

Heat distortion

temperature is the

temperature at which a

sample deflects by 0.1

in. (2.5 mm).

Standard test methods

include ASTM D648,

BS 2782 method 102, ISO R75

การปรบปรงคา HDT ของพลาสตกชวภาพ

PLA มคาอณหภมโกงตวดวยความรอน (Heat distortion temperature,

HDT) ประมาณ 66-76 องศาเซลเซยส (S. Serizawa, 2005, S. Ray, 2003)

PBS มคาอณหภมโกงตวดวยความรอน (HDT) ประมาณ 88-90 องศาเซลเซยส

56

ซงต ากวาอณหภมน ารอน

Melt flow index (MFI) test

Melt index of plastics. The test measures the rate of flow of

polymer melt. It provides an indication of ease of processing.

Standard test methods include ASTM D1238, BS 2782 method 105C, ISO R292

Applications of MFI test

• Suitable materials selection for some

processing techniques

• Indirect evidence of some changes in

molecular structure of polymer chains (e.g.

chain scission)

Applications of MFI test

Time (min) Temperature ( C) Melt flow index (g/10 min)

7 170 23.3 (±3.3)

12 170 29.0 (±5.1)

12 180 44.7 (±6.3)

12 190 57.0 (±6.2)

Table IV Melt flow index of various PLA/MTPS (70/30

%w/w) blends

Effect of MFI and die temperature on polymer process-ability

145 C

125-135 C

115 C

Polymer characterization and analysis

1. Polymer identification • Simple

• Quick

• inexpensive

2. Chemical and thermal analysis (instrumental analysis) Need to understand fundamental and theory of each technique

Some techniques are time consuming, e.g. DSC (scanning rate ~ 10-20 C/min)

Expensive instruments

Polymer Identification Chart

Unknown polymer

Thermoplastics Thermosets

Self-extinguished

Melamine formaldehyde

Phenol formaldehyde

Urea formaldehyde

Continue to burn

Polyester

Silicone Epoxy

PP, PE All others

No flame

Continue to burn

Self-extinguish

Drips, CTFE Drips,

ABS, Polyester, PS, Drips,

Nylons, PC No drips, PTFE, PVF No drips,

PU, cellulose nitrate No drips PVC, PPO

Observations from burning test

• Does the materials burn ?

• Color of flame

• Odor (be careful)

• Does the materials drip while burning?

• Nature of smoke and color of smoke

• The presence of soot in the air

• Self-extinguish or continue to burn?

• pH value of the gas obtained from burning

Characteristics of some polymers observed from burning test

Observations PE PP CFTE PTFE PVF

Color of flame Blue with yellow tip

Blue with yellow tip

- - -

Odor Paraffin Acrid,

Diesel fume

Acetic acid Burnt hair Acidic (HF)

Speed of burning* Fast Slow - - -

Other characteristics

Melt & drip - - - -

Characteristics of some polymers observed from burning test (continued)

Observations ABS Acetal Cellulose acetate

PS Polyester

Color of flame Blue with

yellow edges

Blue Yellow with spark

Yellow Yellow with blue edges

Odor Acrid Formaldehyde

Vinegar Illuminating or marigold

Burning rubber

Speed of burning* Slow Slow Slow Fast Fast


Black

smoke with soot

No smoke Black

smoke with soot

Dense

smoke with soot

Black

smoke with soot


Observations PU Nylon PC PPO PVC

Color of flame Yellow Blue with yellow tip

Orange or yellow

Yellowish orange

Yellow with green edges

Odor Faint (weak smell) apple

Burnt wool or hair

Phenol Phenol Hydrochloric acid

Speed of burning*

Fast Slow Slow Slow Slow


Sample burn completely

Froths Black

smoke with soot

Difficult to

ignite smoke

White smoke


Observations Melamine formaldehyde

Phenol formaldehyde

Urea formaldehyde

silicone epoxy

Color of flame Yellow with blue tip

Yellow Yellow with

greenish blue edge

Bright yellow

Yellow

Odor Fish like Phenol Formaldehyde None Pungent

(strong smell) amine


Swells and cracks

May or may not

be self-extinguish

Swells and cracks

Continue to burn

Black smoke

pH values of some product obtained from burning of polymers

Litmus paper

Red Essentially unchanged Blue

pH paper

0.5-4.0 5.0-5.5 8.0-9.5

PET Polyolefins Polyamides

Unsat. polyester PVOH ABS

Fluorine containing polymers

PVAc Phenolic resin

Styrene polymers (including SAN)

Amino resin (melamine- and urea-formaldehyde

PMMA

PC

Linear PU

Solubility of some common polymers

Polymers Soluble in Insoluble in

PE Xylene (boiling) Alcohols, esters, halogenated HC

PP Chloroform, xylene (above 80 °C)

Alcohols, esters

PVC Dimethyl formamide, THF, Cyclohexanone

Alcohols, hydrocarbons

PTFE Insoluble All solvent

PS Benzene, ethyl acetate Alcohols, water, acetone

Polyisoprene Benzene, toluene Alcohols, esters, ketones

PMMA Aromatic HC, chlorinated HC, esters, ketone

Aliphatic HC, alcohols, ethers

PVOH Formamide, water Aliphatic and aromatic

HC, alcohols, esters, ketone

Solubility of some common polymers

Polymers Soluble in Insoluble in

Polycarbonate Chlorinated HCs, cyclohexanone, DMF, cresol

Only swelling in usual solvents

Nylon Formic acid, phenols Alcohols, esters, HCs

Phenolic resin Benzylamine (at 200 °C) All common solvents

Polyurethane (uncured) DMF Petroleum ether, benzene, alcohols, ethers

Epoxy resin (uncured) Alcohols, ketones, esters, dioxane

Aliphatic HCs, water

Polyacrylonitrile DMF Alcohols, esters, ketones, HCs

NR Aromatic HCs, chlorinated HC

Petroleum ether, alcohol, ketones, esters

SBR Ethyl acetate, benzene, methylene chloride

Alcohols, water

Safety concerns

• Sources of dangerous during the test include – Solvents flame-ability

– Solvents toxicity

– Burning drip

– Burning gas

• How to avoid such the dangerous? – Avoid direct contact by keep working in fume hood

– Wear appropriate dress (lab gown, glove, eyeglasses)

– Keep flammable solvents out of fire source

– Do not dispose used solvents into sink

MTT 552 Polymer Characterization and analysis point... · - Demonstration on the characterization...

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Transcript of MTT 552 Polymer Characterization and analysis point... · - Demonstration on the characterization...