Analysis of Rubber Without Using

Instrument*
Eng Aik Hwee
K&W Training & Consulting
engaikhwee@gmail.com

*For educational purposes only

1
 Objectives
• To introduce some simple experimental analyses without using instrument

Introduction
Reasons for no instrument / not using instrument
• Instrument is expensive to buy
• Expensive to maintain
• Not in production factory
• Not frequently used
• Operating procedure not available
• Operating procedure too complicated
• Not technically competent to operate
2
 Caution:
• Take all the necessary precautions to ensure that it is safe to conduct the experiments
• Wear the necessary personal protective equipment such as goggle, gloves, lab coat
• Make sure that the area is well ventilated
• Ensure that no one is using any naked flame when using solvents
• Always have a second person ready to help in time of emergency

3
 Rubber Density - Objectives
• Determine the rubber density with simple experimental set up
Rubber Density - Introduction
• Used in calculation of many parameters, such as volume, volume fraction, and mass
• ISO 2781 method
• Based on the Archimedes’ [aa-kuh-mee-deez] principle
• The suspension of the solid in a liquid is the easiest method to perform
• Others are Pycnometer methods (rubber > liquid) and mixed liquid method

4
Rubber Density – Archimedes’ Principle
• Any object completely or partially submerged in a fluid (gas or
liquid) at rest is acted upon by an upward, or buoyant, force.
• Force = Weight of the fluid displaced by the object.
• Volume = Volume of the object below the liquid surface.

5
 Rubber Density – 1) Pycnometer Method
1) a) Weight loss in liquid = Weight of liquid displaced
= Density x volume of liquid displaced ( x v)
mfw – (mfwp (mfw + weight in
= {mfw – (mfwp – mp)}
liquid ) - mp)}
b) Volume of rubber v = {mfw – (mfwp – mp)}/
c) Density of rubber = mp/v
Suitable for object > liquid where mfw < mfwp
For object < liquid
mfw = mfwp

6
2) Rubber Density – Suspension Method
1) Metal piece (A) replaces displaced water (B)
2) Volume of metal piece = Volume of displaced water
= Weight of water/density of water
3) When water is not drained out, the container weight increases by 2kg

(A)

Shut side drain

5kg Load
(B)
volume
2kg

7
 Rubber Density – Methods
2) a) Measure the weight in air = mp
b) Measure the increase in liquid weight when suspending the rubber in the liquid = ml
= Weight of liquid displaced
c) Volume of rubber v = volume of liquid displaced
= ml/density of liquid displaced
v = ml/
d) Density of rubber = mp/v

8
Rubber Density – 3) Mixed Liquids Method
3) a) Mix a higher density liquid to a less one with a rubber until it becomes suspended
b) Determine the density of the mixed liquids by a pycnometer or densimeter

Known volume

Some Practical Notes

1) The rubber sample must not absorb the liquid used. Lower surface area better
2) The rubber sample must not trap air bubbles
3) Density is a temperature dependent properties, higher at lower temperature and
vice versa
4) For pycnometer method (method 1), object density should be higher than liquid
density 9
Video on Density Measurement (Suspension Method)

10
 Question 1: In the diagram below, what is the weight
registered by the weighing balance when a 5kg load is being
suspended in the water. ?kg =
(A) 18kg, (B) 20kg, (C) 23kg, (D) 25kg
Question 2: If the weight of a load in the air is
500g, the volume of liquid with a density of
0.9g/cm3 displaced from the container is
300cm3, when the load is weighed in the
liquid, what is the weight of the load in the
liquid?
(A) 500g, (B) 270g, (C) 230g (D) 200g

Weight =20kg Weight = ?kg Weighing balance 11

Question 2: If the weight of a load in the air is 500g, the volume of liquid with a
density of 0.9g/cm3 displaced from the container is 300cm3, when the load is weighed
in the liquid, what is the weight of the load in the liquid?
(A) 500g, (B) 270g, (C) 230g (D) 200g

12
 Crosslink Density of Rubber Using Swelling Method
Objective:
To determine crosslink density of rubber using solvent swelling method
Introduction:
• Rubber requires crosslinks to enhance its mechanical and chemical properties for a
longer service life
• Increase in crosslink density will not enhance the rubber performance indefinitely
• There will be certain optimum level of crosslink density for optimum product
performance
• Some examples are given here
• Estimation of crosslink density is essential for product performance and service life

13
Crosslink Density of Rubber and Mechanical Properties
Properties Changes with crosslink density
Friction coefficient, permanent set, Decrease with increasing crosslink
hysteresis density
Hardness, static & dynamic modulus Increase with increasing crosslink density
Tensile & tear strength, toughness, Increase to a maximum value & then
fatigue life decrease

14
 Rubber Crosslink Density

Crosslink density, :
• A measure of crosslinking points per unit volume (normally in mol/cm3). Also in mol/g
• Mc: Average molecular weight of rubber segment between crosslinks (in g/mol).
Correlation:  = 2/(Mc)  (nu)
• where = Density of crosslinked rubber (in g/cm3),
• = 3, 4 for tri- (T) & tetra-functional (+) network
•  = 2/(4Mc) or  = /(2Mc) 15
 Principle of Crosslink Density Measurement

• When in equilibrium, osmotic pressure of solvent in rubber () = Elasticity of rubber ()
• Swelling ratio (Sv) = Vswollen/Vdry
= 1/Vr Vr = Volume fraction of rubber in swollen rubber
Vswollen = Volume of solvent + volume of rubber
(Volume = weight/density) .
16
 Principle of Crosslink Density Measurement
• Osmotic pressure of solvent in a swollen rubber ()
= – (RT/ Vs)[ln(1- Vr) + Vr + Vr2],
low (–)pressure in rubber, high (+) pressure in solvent
• Elasticity of rubber ()
= RT[(Vr)1/3 – ½Vr]  (Nu) = Crosslink density mol/volume (mol/cm3)
= RT[(Sv)-1/3 – ½Sv-1] Vr = Volume fraction of rubber in equilibrium swollen
Sv= Swelling ratio in volume vulcanised rubber sample
= Vswollen/Vdry Vs = Volume per mol of solvent at room temperature
in cm3/mol (from molecular weight and density)
 = Flory-Huggins polymer-solvent interaction
parameter.
17
• When in equilibrium:
•  = : RT [(Vr)1/3 – ½Vr] = - (RT/ Vs)[ln(1- Vr) + Vr + Vr2]
• Because Vr <<1;
• ln(1- Vr)  -Vr – ½ Vr2;
• (Vr)1/3 >> ½Vr
(Vr)1/3 – ½Vr  (Vr)1/3
The simplified Flory-Rehner equation becomes…
(Vr)-5/3 = (Sv)5/3 = (½ - )Vs/  = Crosslink density mol per unit volume (mol/cm3)
Vr = Volume fraction of rubber in equilibrium swollen
• If  from other method, vulcanised rubber sample
 calculated using Vr from Vs = Mole volume of used solvent at room temperature
swelling data in cm3/mol (from molecular weight and density)
 = Flory-Huggins polymer-solvent interaction
parameter. Depends on temperature
18
 Crosslink Density – Experimental Procedure
• Use a good solvent for the maximum swelling.
• Swell the rubber test piece in the dark at room temperature, 3-7 days
• Measure the weight of swollen gel, m3,
• Dry the swollen gel in oven and measure dry rubber weight m1
• Weight of solvent in the swollen rubber m2 = m3-m1
• The volume fraction of the rubber in swollen state, Vr is as follows:
Vr = Volume of rubber/ [(Volume rubber) + (Volume of solvent)]
= (m1/ρ1) / [(m1/ρ1)+ (m2/ρ2)]
m1 = weight of dry polymer sample;
ρ1 = densities of the dry polymer sample
m2 = weights of solvent in the swollen sample;
ρ2 = density solvent
19

• The Flory-Rehner equation::
 = Crosslink density mol per unit volume (mol/cm3)
Vr = Volume fraction of rubber in equilibrium swollen
vulcanised rubber sample
Vs = Mole volume of used solvent at room temperature
in cm3/mol (from molecular weight and density)
 = Flory-Huggins polymer-solvent interaction
parameter.

• For high non-rubber materials such as ZnO, S, filler in the rubber, deduct the volumes
from dry rubber volume
Volume of ZnO, VZnO = Weight of dry ZnO/Density of ZnO
Volume of filler, Vfiller = Weight of dry filler/Density of filler
Net volume of dry rubber = Gross dry rubber volume – Vfiller – VZnO – Vsulfur – …..
• Gross dry rubber volume = Weight of rubber sample/Density of sample
• Total volume = Gross volume of dry rubber + Volume of solvent
• Failing to consider the filler effect will lead to over estimation of crosslink density.20
 Crosslink Density  Calculation – Work it out!
▪ Swollen crosslinked natural rubber + toluene = 0.5169g
▪ Dry natural rubber weight after removing solvent 0.0958g
▪ Molar volume of toluene Vs= 106.29cm3/mol
▪ Density of natural rubber (0.914 g/cm3)
▪ Density of toluene (0.867 g/cm3 )
▪ Polymer-solvent interaction parameter  = 0.393
Vr = Volume of rubber/ [(Volume rubber) + (Volume of solvent)]
= (m1/ρ1) / [(m1/ρ1)+ (m2/ρ2)]
m1 = weight of dry polymer sample;
ρ1 = densities of the dry polymer sample
m2 = weights of solvent in the swollen sample;
ρ2 = density solvent
21
 Solvent Swelling Method – Example of Calculation
▪ Swollen crosslinked natural rubber + toluene = 0.5169g
▪ Dry natural rubber weight after removing solvent 0.0958g
▪ Molar volume of toluene Vs= 106.29cm3/mol
▪ Density of natural rubber (0.914 g/cm3)
▪ Density of toluene (0.867 g/cm3 )
▪ Polymer-solvent interaction parameter  = 0.393
▪ Volume of rubber, a = 0.0958/0.914 cm3
(without any correction for the non-rubbers)
▪ Volume of solvent, b = (0.5169-0.0958)/0.867 cm3
▪ Rubber V fraction Vr = a/(a+b) = (0.0958/0.914)/[(0.0958/0.914)+(0.5169-0.0958)/0.867
= 0.1775
▪  = [loge (1-0.1775) + 0.1775 + (0.393x0.17752)]/[2x106.29x(0.17751/3 – 0.1775/2)]
= 5.5x10-5 mol/cm3
22
 Solvent Swelling: Some Practical Notes
• Use less volatile solvent for a more stable reading
• Better solvent purity, better results, unless for comparison study
• Swelling in the dark to avoid degradation
• Allow sufficient time to reach equivalent
• Repeat for a longer time to see any further swelling increase
• When non-rubbers such as filler is significant, correction is needed in the calculation

23
Video on Solvent Swelling

24
Question 3: For tri-functional network, what is the relationship between crosslinking
points and average molecular weight of rubber segment (Mc)?
(A) Every 3 Mc; 1 crosslinking point
(B) Every 3 Mc; 2 crosslinking points
(C) Every 2 Mc; 3 crosslinking points
(D) Every 1 Mc; 3 crosslinking points

25
Question 3: For tri-functional network, what is the relationship between crosslinking
points and average molecular weight of rubber segment (Mc)?
(A) Every 3 Mc; 1 crosslinking point
(B) Every 3 Mc; 2 crosslinking points
(C) Every 2 Mc; 3 crosslinking points
(D) Every 1 Mc; 3 crosslinking points
Question 4: Based on the simplified Flory-Rehner equation, (Sv)5/3 = (½ - )Vs/
which of the following statements are correct:
i) Swelling ratio (Sv) increases when crosslink density () increases
ii) Swelling ratio (Sv) decreases when crosslink density () increases
iii) Swelling ratio (Sv) increases when interaction parameter () decreases
iv) Swelling ratio (Sv) decreases when interaction parameter () decreases

(A) i & iv (B) ii & iv (C) ii & iii (D) i & iii) 26
Fractionation of Rubber: Objectives
• For obtaining structural information, e.g. branching functional group
distribution
• For obtaining rubber with narrow molecular weight distribution (MWD) to study
relationships between structure and properties
• For understanding the processing behaviour of rubbers of different MW
• For elucidating mechanisms of rubber formation, e.g. terminal groups (high
concentration) in low MW natural rubber
• For understanding of some physical properties such as solvent and oil
resistance and crystallinity

27
Fractionation of Rubber: Introduction
• Rubber molecules are more soluble at elevated temperature
• High molecular weight (MW) rubbers of low polarity are less soluble:
a) at lower temperature
b) in the presence of polar solvent (poor solvent)
• Addition of poor solvent cause precipitation of high MW weight rubbers
• Instant precipitation may be due to the “localised effects”
• Increasing temperature redissolves the precipitated rubber
• Slow cooling selectively precipitated the high MW rubbers without the “localised
effects”

28
Experimental Set Up

Poor solvent, e.g. methanol

Overhead stirrer

Rubber in solvent
e.g. toluene Thermostatic water bath, e.g.
at 30oC

Thermometer
Thermostat sensor
Folding
propeller
29
 Fractionation: Experimental Procedure Thin rubber
sheet

1) Dissolve raw natural rubber in a solvent, e.g. toluene at 1% w/v,

Required: Raw natural rubber, toluene, beaker, magnetic stirrer & bar
2) Centrifuge (preferred) or filter with a glass filter to remove gel Rubber
Required: Sintered glass filter no 2, or centrifuge machine band

3) Transfer to a pear shape glassware

Required: 2-neck pear shape glassware, 500ml
4) Place it in a thermostatic water bath, temperature 30oC
Required: Thermostatic water bath, thermometer, overhead stirrer, propeller
5) Add a poor solvent, e.g. methanol until cloudy, or rubber precipitated.
Figure 1
Require: Methanol
6) Raise the bath to 35-40oC while stirring until the solution turns clear.
30
 Fractionation: Experimental Procedure
7) Stop stirring, set the bath back to 30oC, allow it to cool to 30oC over night
8) Upon cooling, a small amount of rubber appears at the bottom, Figure 2.
9) Remove the clear rubber solution, dissolve the rubber at the bottom in the solvent, add
it to excess poor solvent such as methanol and dried at reduced pressure.
Required: Vacuum chamber
10) This fraction contains the highest molecular weight rubbers
11) Pour back the rubber solution to the container and repeat the Steps 5-9, until all the
rubber fractions have been isolated.
12) When no rubber is precipitated at the end, concentrate the rubber solution by
evaporation, repeat Steps 5-9, or add it to the poor solvent to obtain the last fraction.

31
Precipitated Rubber After Cooling

Folding
propeller

Precipitated rubber

32
 Fractionation of Rubber: Process Flow
Dissolve rubber in a solvent Remove gel Add poor solvent + Stirring

Remove clear Slow cooling to Increase temperature to

rubber solution precipitate rubber dissolve precipitated rubber

Dissolve precipitated Re-precipitated in Dry rubber under

rubber in the solvent excess poor solvent reduced pressure

33
 Example of Applications:
Fraction Aldehyde groups per chain*
1 1.2
2 1.1
3 1.1
4 0.4
*2,4-dinitrophenylhydrazine method.
http://vitaldoc.lgm.gov.my:8060/vital/access/services/Download/vital1:24302/ARTICLE

Aldehyde groups in degraded rubber are expected to be concentrated in low MW

Inference: The low aldehyde content in low MW fraction indicates that it is not
derived from oxidative degradation reactions.
34
Fractionation of Rubber: Some Practical Notes
• Use soluble fraction only
• Rubber concentration < 1% w/v
• Fraction weight depends on molecular weight distribution
• Amount of poor solvent needed is by experience
• Slow addition of poor solvent to allow good mixing and to prevent precipitation
of large amount of rubber
• Reprecipitation of isolated rubber to remove the mixed low MW rubbers
• Antioxidant may be added to prevent degradation, if it does not affect the
subsequent test results

35
Video on Fractionation
Question 5: In the fractionation of rubber experiment, which of the following
statements are true.
i) When the water bath temperature is gradually increased to re-dissolve the
precipitated rubbers, high molecular weight rubbers will dissolve first, followed by
low molecular weight rubbers
ii) When the water bath temperature is gradually increased to re-dissolve the
precipitated rubbers, low molecular weight rubbers will dissolve first, followed by
high molecular weight rubbers
iii) When rubber solution is added to excess poor solvent, the lowest molecular
weight rubbers may not be precipitated, if the solution concentration is too low
iv) When rubber solution is added to excess poor solvent, the highest molecular
weight rubbers may not be precipitated, if the solution concentration is too low

(A) i & iii (B) i & iv (C) ii & iii (D) ii & iv
Intrinsic viscosity, viscosity-average molecular weight (Mv), Huggins
constant, constant in Mark-Houwink equation
 Introduction
• Intrinsic Viscosity (IV) is a measure of the polymers molecular weight
• Reflects the material’s melting point, crystallinity, and tensile strength.
• Glass transition temperature, Tg= Tg (∞) – K/M
• Significantly affect the physical (e.g. softness), mechanical properties and
processability of the materials.
Example
• Better tensile with bimodal MWD of polyisoprene rubber in the latex.
• Ref: US Patent 11084918 (2021)
“A synthetic polyisoprene latex containing synthetic polyisoprene with a low-molecular
weight polyisoprene of less than 1,000,000 at a content rate of 10 to 70% by weight
and a high-molecular weight polyisoprene of 1,000,000 or more at a content rate of 30
to 90% by weight.”
 Objectives
• Measure intrinsic viscosity (IV) of rubber / polymer solution
• Calculate the molecular weight from IV data and Mark-Houwink constants
• Determine the Huggins constant and demonstrate its relationship with rubber /
polymer branching
Experimental Set Up
 Experimental Procedure
1) Dissolve the rubber in a rubber solvent at 0.5% w/v
2) Filter the rubber solution with a glass filter
3) Pour solvent / rubber solution into the viscometer via opening (1)
4) Allow the liquid temperature to reach equivalent in the water bath.
5) Shut opening (2) first, then apply positive pressure (e.g. via any
compressed gas) to opening (1) to pump the liquid in (3) up to
above level (A).
[For easy operation, modify (1) and (2) to Quick-fit joints]
6) Release the pressure on (1) first, and then open (2)
7) Measure the flow time point (A) to (B) in a water bath set at 30oC
8) Repeat several times to obtain consistent readings
9) Dilute the rubber solution and determine the flow time
10) Calculate sp (Specific viscosity) = (trubber−tsolvent) /tsolvent
43
Data Processing
1) Huggins equation is shown in Equation 2.
sp/c = [] + k’ []2c
where c = Concentration of the rubber solution in g/dl-1,
[] = Intrinsic viscosity,
k’ = Huggins constant.
sp = Specific viscosity = r – 1 In practice, ηr = t / to
r = Relative viscosity =  /o and ηsp= (t−to) /to
 = Viscosity of rubber solution where t = Rubber solution
in solvent flow time in a viscometer
o = Viscosity of pure solvent = ηr - 1
2) Plot sp/c versus c, [] from the intercept to= Pure solvent flow
3) k’ calculated from the gradient time in a viscometer
44
 Data Processing
4) From the Mark-Houwink equation:
[] = KMva, where “K” and “a” are the Mark-Houwink constants,
Mv = Viscosity average molecular weight, can be calculated using the “K” and “a”
values from the literature
5) If the molecular weight of each fraction of fractionated rubber is known using other
methods, ‘K’, and ‘a’ can be calculated.
6) For polydisperse rubber Mn < Mv < Mw
Mn = Number average MW; Mw = Weight average MW
7) For fractionated samples with narrow MW distribution, Mn  Mv  Mw
8) Degree of polymerisation = Molecular weight of rubber / MW of repeating unit
9) k’, the Huggins constant is independent of molecular weight;
- increases with decreasing solvent power,
- increases with branching
[Bristow GM (1962) The Huggin’s ’ Parameter for Polyisoprenes. J. Polym. Sci. 62:S168-S171.]
45
Example of Application
Fraction Intrinsic Huggins Molecular weight, Mn x 10-5 Branching**
viscosity, [] constant, k’ Osmometry 13C-NMR*

1 8.0 0.82 10.9 1.79 5.1

2 7.5 0.80 8.7 1.69 4.1
3 5.2 0.75 6.1 1.37 3.4
4 1.1 0.40 0.7 0.41 0.8
*Based on peak intensity ratio of cis/trans isoprene
**Branching = Mn (Osmometry)/Mn(NMR) – 1
[] = KMa => Log [] = Log K + a LogM Plot Log [] versus LogM
46
Example of Application
K x 104 a
Literature 3.31 0.71
Example 2.99 0.74

47
Intrinsic Viscosity: Some Practical Notes
• Use soluble fraction only
• Filtered rubber concentration < 0.5% w/v
• Solution must be dust free
• Dust causes inconsistent flowing time
• Viscometer should not be dried in oven. Blow dry is better

48
Video on Intrinsic Viscosity Measurement

49
Question 6: Which of the following parameters is not needed in the calculation of
viscosity average molecular weight using the viscometer method?

(A) Mark-Houwink Constant (a)

(B) Mark-Houwink Constant (K)
(C) Huggins Constant (k’)
(D) Intrinsic viscosity []

50
Question 6: Which of the following parameters is not needed in the calculation of
viscosity average molecular weight using the viscometer method?
(A) Mark-Houwink Constant (a)
(B) Mark-Houwink Constant (K)
(C) Huggins Constant (k’)
(D) Intrinsic viscosity []

Question 7: Which of the following statements is true.

(A) Intrinsic viscosity is inversely proportional to viscosity average molecular weight of rubber
(B) The flow time of a pure solvent is longer than that of rubber solution in the solvent
(C) Huggins Constant (k’) is equal to the gradient of the plot sp/c versus c, where c is the rubber
concentration and sp is the specific viscosity
(D) Viscosity molecular weight (Mv) falls between number average MW and weight average MW
51
End of Presentation. Thank You

52
IR | Unknown Polymer and or Rubber Sample
Identification

Many samples of unknown composition

IR SPECTRA

October 4, 2022
04.10.2022 Innovation with Integrity 53
IR | Quantification of Polymer and or Rubber
Blends

Quantification of compounds helps characterize product properties

Blend PP LDPE
1 93 % 0%
2 83 % 10 %
3 73 % 20 % Polypropylene
Polyethylene
4 63 % 30 %
5 93 % 40 %
6 0% 93 %

Concentration:
Concentration: 0 to0 93%
to 93%
Correlation:0.999
Correlation: 0.999
Sigma:
Sigma: 1.88
1.65

October 4, 2022
04.10.2022 Innovation with Integrity 54