mtt 552 polymer characterization and analysis point... · izod impact test 3. falling weight test...
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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 %
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)
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
Conversion to Stress-Strain
• Stress (N/m2 or Pa) = Force / Cross-sectional Area
• Strain (dimensionless) = Displacement / Initial length = L/Lo
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
Results from stress-strain curve
• Tensile strength at Break (MPa)
• Ultimate Tensile stress (MPa)
• Elongation (%) • Modulus (MPa) • Toughness (Nm)
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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)
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
Impact test Izod impact strength = (E1-E2)/thickness
Standard test methods include
•ASTMD256; •BS2782 (method 306A) •ISO R180
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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)
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
Falling weight test
Falling weight impact strength = (W)(H)
Standard test method include BS 2782 method 306B
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
09/08/55 Dr. Jatuphorn Wootthikanokkhan, KMUTT
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
Peel test Peel strength (N/m) = Force/strip width
Failure mode is also important
• Cohesive failure • Adhesive failure
Determination of adhesion between EVA and glass substrate by 180 degree peeling 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
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
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
Other characteristics
Black
smoke with soot
No smoke Black
smoke with soot
Dense
smoke with soot
Black
smoke with soot
Characteristics of some polymers observed from burning test (continued)
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
Other characteristics
Sample burn completely
Froths Black
smoke with soot
Difficult to
ignite smoke
White smoke
Characteristics of some polymers observed from burning test (continued)
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
Other characteristics
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