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Polymer Chemistry PDF
Polymer Chemistry PDF
EXPERIMENT 1 Identification of Polymers from Solubility Tests Introduction A macromolecule becomes a single phase in solution according to the same thermodynamics laws as the micromolecular solution substances. However, differences in molecular size influence the solubility properties of both these substances. For example, a macromolecule dissolves slowly due to its entangled constitution opposing the penetration of the solvent; but most polymer-solvent pairs can mix in all of the proportions. On contrary, though micromolecular substances normally are much easier to dissolve than the polymer, the solubility of micromolecules is generally limited to saturated solution. The solvent of a macromolecule can be considered good by one of these two standards, i. e. the kinetic standard or the thermodynamic standard. A good solvent from the kinetic point of view is a solvent that easily dissolves the polymer in a short time. The solubility can be made faster by decreasing the particle size of the polymer sample because more of its surfaces are exposed to the solution. From the thermodynamic point of view, a good solvent has to be able to strongly interact with the solution substances due to it similarity in their chemical structure. Thus, a good solvent in terms of kinetics is fast while that in terms of thermodynamics is efficient. An amorphous polymer contains a network of entangled, flexible chains in a continuous motion. When the polymer is sunk in a solvent, the polymer network will swell from the osmotic activity of the solvent; the segmental motion will finally increase. Provided the solvent is still available, the polymer will continue to expand and increase its freedom to move. When the solvation process has sufficiently advanced to allow transitional movement to the chains, the substances will separate out to form a solution. Consequently, as the solution becomes more diluted, the intermolecular forces that exist between the polymer chains will become less and finally the solution properties will only exhibit polymer-solvent interaction forces. Solubility of a polymer will happen if the free energy of the solution (G) is given by: G = H - TS (1)
is negative. Entropy of the solution (S) is normally small but positive, thus the sign and magnitude of the enthalpy of the solution (H) will determine whether the dissolution process can happen or not. Scatchard-Hildebrand equation can be written as H / Vsp = (s - p)2 (2)
where V is the total volume of the mixture, s and p are the volume fractions of the solvent and polymer respectively, while s and p are the solubility parameters of the solvent and polymer respectively. Generally, if (s - p) = 0, equation (2) will show H = 0 and the dissolution process will happen because of the S factor. Solvent solubility parameter can be calculated fr - 1 -om the expression
where Hv is the molar heat of vapourization, M and d are the molecular mass and density of solvent respectively. Polymer solubility parameter is obtained from: p = d G/M (4)
where d is the density of polymer with repeating units of molecular mass M, and G is the molar attraction constants (see Table 1.1). Here, refers to the total of all the chemical structure groups in the repeating unit of the polymer. Normally without strong interactions like hydrogen bonds, the solubility of a polymer can be predicted if s - p < 1. Calculation Example Polymer: poly(vinyl acetate) = -[-CH2CH(OCOCH3)-]nDensity = 1.19 g cm-3 Molecular mass of repeating unit = 86.1 g mol-1 Group 1 -CH3 1 -CH2 1 -CH 1 -COO G = p G (J1/2 cm3/2 mol-1) 420 280 140 512______ 1,352
= _______density x G_________ molecular mass of repeating unit = (1.19 x 1,352) 86.1 = 18.7 J1/2 cm3/2
Method Each student is provided with 2 polymer samples to identify. Place ~0.001 g of the polymer sample in a test-tube of measurement (13 x 100 mm) and add 5 mL of the solvent required for the test. The dissolution process can be made faster whenever necessary by heating the test-tube in a hot water-bath in the fume cupboard. The solubility test is considered negative if, after stirring once a while with a glass rod, two phases still remain after 5 min of heating at the boiling point of the solution, or the two phases are formed from the solution while cooling it to room temperature. A polymer sample can be found in the following flow-chart which must be used as guide. When the arm of the flow chart shows towards the right, the polymer will dissolve or the test is positive; and when the arm shows towards the left, the polymer will show the opposite result.
Table 1.2 Density (g cm-3) of Polymers Polymer Ethyl cellulose Polyamide-6,6 Poly(ethylene) Poly(isobutylene) Poly(carbonate) Poly(methyl methacrylate) Poly(oxymethylene) Isotactic poly(propylene) Poly(styrene) Poly(tetrafluoroethyllene) Poly(vinyl alcohol) Poly(vinyl acetate) Poly(vinyl chloride) Poly(vinyl pyrolydone) Code EC PA66 PE PIB PC PMMA POM PP PS PTFE PVAl PVAc PVC PVPy Amorphous 1.15 1.09 0.85 0.91 1.20 1.17 1.25 0.85 1.05 2.00 1.29 1.19 1.41 1.25 Crystalline 1.24 1.00 1.94 1.23 0.94 1.12 2.40 1.35 1.44 -
Note: s = strong hydrogen bonding m = moderate hydrogen bonding p = poor hydrogen bonding Flow-chart to identify polymer from solubility test
Sample Insoluble Toluene Cyclohexanone Cresole DMF Xylene Chloroform POM PP/PE (soluble in toluene and xylene, T>80oC) PTFE PC (slowly soluble in) cyclohexanone) Ethyl acetate PVAc (soluble in cold toluene) EC (soluble in hot toluene) PVC polyamide Methanol PVAl PVPy Water Soluble Chloroform
Note: EC = ethyl cellulose PVAl = poly(vinyl alcohol) POM = polyoxymethylene PE = polyethylene PVC = poly(vinyl chloride) PTFE = polytetrafluoroethylene
PMMA = poly(methyl methacrylate) PC = polycarbonate PVAc = poly(vinyl acetate) PP = polypropylene PIB = polyisobutylene PVP = poly(vinyl pyrolydone)
PS = polystyrene
Note In the case of polymer with an unknown molecular mass, the extinction coefficient is reported as the mole of the repeating unit. For example, in this case, the repeating unit of poly(methyl metacrylate) is CH2-C(CH3)COOCH3- and is equivalent to molecular mass of 100. Data Analysis Beers Law : A =
.b.c
= Molar extinction coefficient b = Cell distance (in this case, b = 1 cm) c = Concentration (mol dm-3)
(b) Emulsion polymerization Into each of the glass bottle add: (i) 60.0 ml distilled water, (ii) 0.0300 g K2S2O8 (fill in actual weight used into the table), (iii) 0.0300 g Na2HPO4 (fill in actual weight used into the table) and (iv) Surfactant, SLS or SDS (as stated in the table) Shake the flask slowly until all the chemicals dissolved in the water. Add 15 ml styrene to each of the bottle, and immediately bubbled nitrogen gas through the mixture for 2 minutes and quickly cap the bottle. Shake vigorously to mix the monomer and the aqueous phase to form emulsion (look like milk or latex). Claim bottles in water bath, set to temperature (as specified by the lecturer) at 60 - 80C. Allow for 1 minute for the content to reach the temperature of the bath and start timing the reaction. Every 15 minutes, take the bottles up for shaking 20 seconds, and immediately put back into the bath. N K2S2O8 o. 1 2 3 4 5 6 7 8 9 10 11 12 Na2HPO4 Surfactant/g 0.0600 0.0800 0.1000 0.1200 0.1500 0.1800 0.2100 0.2500 0.3000 0.3500 0.4000 0.5000 [surfactant] Styrene Wt of PS 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml 15 ml
EXPERIMENT 4 Preparation of Polyester by Condensation Polymerization Introduction Differences between step and chain polymerizations The distinction between step and chain polymerization is an important concept in polymer chemistry. Firstly, in step polymerization, any two molecules in the system can react with each other. Initially, the monomers react to form dimers, dimers can react with dimers to form tetramers and so on. On the other hand, in chain polymerization, chain growth takes place only at the reactive terminals of a few initiated chains. Secondly, as a result of this difference, step reactions are characterized by a disappearance of the monomer at end early stage of the polymerization, and by the existence of a broad molecular-weight distribution in the later stages of the reaction. With chain polymerizations, the monomer concentration decreases steadily throughout the reaction and, ideally, at any stage the reaction mixture contains only monomer and high polymer. Thirdly, the variation in molecular weight at different stages in the reaction provides another distinguishing feature. In step reactions the polymer molecular weight increases slowly and steadily with the degree of conversion. In a chain reaction, high polymer is formed rapidly from each initiated monomer. Hence the molecular weight of each polymer molecule does not increase appreciably after the initial rapid propagation. At longer reaction time, there may be an increase in the number of polymer molecules, but not in the molecular weight of those already formed.
Polyester In principle a polyester can be produced from a monomer that has both OH and COOH functional groups, such as the lactic acid. The general reaction is represented by HO-R-COOH + HO-R-COOH HO-R-COR-COOH + H2O || O
HO-(R-CO-R)n-COOH + (n-1)H2O || O Such types of monomers are difficult to obtain in pure state, since reaction can begin even when the monomer is being stored. In addition, the control of molecular weight of the polyester becomes very difficult to achieve.
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+ (n-1)H2O
Examples of some well known commercially important polyester are PET, PBT, PC and alkyds.
The Basic Carothers Equation For simplicity, we consider the synthesis of polyester from equimolar amounts of a diol and a diacid. One molecule of diol contains 2 groups of OH, and the functionality f = 2. The diacid (dicarboxylic) molecule contains 2 groups of COOH , and the functionality f = 2. { for a triol, f=3 .} Initially, Ao and Co represents the total OH and COOH groups respectively O O || || HO-R-OH + HOOC-R-COOH H-[O-R-O-C-R-C-]nOH + H2O Ao= 1/2 Uo Co= 1/2 Uo 0 0
where 1/2 Uo = number of diol molecules = number of diacid molecules total number of hydroxyl group, Ao = 1/2 Uof = Uo total carboxylic group, Co = 1/2Uof= Uo no. ester group, Zo = 0 no. water formed, Wo = 0 At time t, A and C represent the remaining OH and COOH groups respectively, and the polymerization medium might contain a mixture of the various chain length as follows: HO---COOH HO----COOH HO------COOH HO-------COOH HO-------------COOH .... The extent of reaction (polymerization) p would be given by p amount functional group that have reacted initial amount of functional group
p = (Co - C) /Co = (Ao - A)/Ao Co = Ao = Uo, dan C = A, Hence p = (Co - C) /Uo = (Uo - A)/Uo
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One -OH and -COOH react to produce one ester linkage and evolve one water molecule, Hence (Ao-A) -OH and same number of -COOH would produce (Ao-A) ester linkages (Z) and (Ao-A) molecule of water (W). Z = W = (Ao-A) = p Uo
Average degree of polymerization Pn The polymer molecules formed at any time t would not be of the same molecular weight (or same chain length). The average degree of polymerization can be estimated from the extent of polymerization p.
Total number of polymer chain Nt = total number of end-groups (since each polymer chain has 2 ends) Nt = 1/2 (C+A) = (1-p)Uo Total amount of monomers 1/2C0+1/2A0 = U0 , and these would become the total number of repeating units in the polymers. Average degree of polymerization, Pn = total number of repeat units / number of polymer chains = Uo/Nt = Uo /{(1-p)Uo} = 1/(1-p) Pn = 1/(1-p) The relationship between Pn and p : p Pn 0 1 0.5 2 0.75 4 0.9 10 0.95 20 0.99 100 0.999 1 1000 Basic Carothers equation
In this experiment, we are going to make polyester from phthalic anhydride and ethylene glycol, and keep the extent of reaction p between 60-80%, so that the polymer would have a low degree of polymerization. 2 < Pn < 10. The resulting polyester would be in the form of a vicious liquid. Stage 1: HO-CH2CH2-OH + C6H4(CO)2O HO-CH2CH2-OOC-C6H4COOH [62] [148.2] bp198 mp131, bp284 + no water
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Figure 2
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The Ubbelohde type of viscometer is the most convenient to use in that it is not necessary to have exact volumes of solution to obtain reproducible results. Furthermore, additional solvent can be added (as long as the total volume can be accommodated by the reservoir); thus concentration can be reduced without having to empty and refill the viscometer. CAUTION: It is necessary to ensure that the polymer solution is free from and solid particle, either due to dust or incompletely dissolved polymer, as any particle that got stuck at the capillary tube would affect the flow time.
Viscosity can be expressed in several ways as described below. Relative viscosity r Relative viscosity is the ratio of solution viscosity to solvent viscosity, which is proportional to a first approximation for dilute solutions to the ratio of the solution flow time to solvent flow time.
r =
= 0
t t0
(1)
where and 0 are the viscosities of the solution and solvent respectively; t and t0 are the respective flow time of the solution and the solvent respectively.
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sp
- 0
0
t - t0 t0
r - 1
(2)
Both r and sp are dimensionless (i.e. without a unit). As concentration increases, so does viscosity. Hence to account for the concentration effects, the specific viscosity is divided by concentration to give the reduced viscosity, red
re d =
s p c
(3)
Not uncommonly, viscosities are determined at a single concentration and the inherent viscosity (inh) as defined below is used as an approximate indication of molecular weight.
inh
ln r c
(4)
where concentration c is commonly expressed as g per 100 ml. The change in solution viscosity with increasing concentration can be expressed as a series in concentration c as given by the Huggins Equation and the Kraemer equation as shown below.
sp c
[ ] + k 1 [] c
2
(5)
ln r c
2 [ ] - k 1' [ ] c
(6)
[ E. D. Kraemer, Ind. Eng. Chem., 30(1938) 1200] Both the inherent and reduced viscosities extrapolate to give the intrinsic viscosity, [], at zero concentration.
[]
sp
c=0
ln c
(7)
c=0
The Huggins constant k1 is related to the molecular structure and the degree of association of the polymer chains in the solvent. It could be shown mathematically that the two equations (5 & 6) would converge to intercept at the y-axis to the same [ ] and k1 + k = (8)
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Average of three most consistent measurement = c g/100 ml Solution flow time /s 1 2 3 4 Average t
r = t/t0
sp
sp/c
Ln r/c
Plot (sp/c) and (ln r /c ) versus c in the same graph paper, and determine the intrinsic viscosity [ ]. Determine the viscosity average molecular weight of your polystyrene sample. The intrinsic viscosity of a polymer is related to the viscosity average molecular weight by the Mark-Houwink Equation. [ ] = K (Mv)a (9)
where K and a are constants for a specific polymer and are dependent on the temperature and solvent. In the case of polystyrene in toluene at 30C, K = 9.2 x 10-3 ml g-1 and a = 0.72.
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The first step in running VPO is to ensure that the sample chamber is saturated with solvent vapour at a certain temperature. Thermistor is a smart device that can measure temperature (T) change as low as ~10-5 K. Two wicks, one for polymer solution (PS) and the other for pure solvent (S) are used to attach one drop of PS to one end of the thermistor and one drop of S of the same size to the end of other thermistor. According to Raoults Law for ideal solution, the drop in partial vapour pressure of the solvent PS drop is lower than that of the solution S. Therefore, the vapour of the solution from the gas phase will condense at the PS drop. This condensation process releases heat energy, thus the temperature of PS will increase. Due to the excess amount of solvent in this system, evaporation and freezing of S drop can be ignored. The temperature difference ( T) between both thermistors mentioned above is proportional to the difference in electrical resistance ( R) measured electronically. In nonequilibrium system, there is a semi-empirical relationship between dilute PS with concentration, c (g/kg),
1 R = K M + Bc c n
(1)
where K is the cell constant and B is the parameter that relate to the second virial coefficient [2].
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R c
'
2 = K 1 + M o Bc '
(2)
where c' = c/Mo (mol/kg). Intercept derived from the linear-plot of R/c' versus c' gives K. If a best fit straight line is made according to equation (1) gives an intercept of I, then
Mn =
K I
(3)
Operational procedures In this experiment, VPO Osmomat O7O-B (calibrated with benzyl, Mo = 210.23 g/mol) will be used. The calibration data are: Solvent Temperature (cell set pt.), T Concentration, c (g/50 g) = = = toluene 45.0oC 0.04, 0.07, 0.10 and 0.13
Students must work in a group of two. Prepare four standard solutions of poly( -methyl styrene) (PAMS) in toluene with concentration as shown below: Series 1 2 3 Sample PAMS H M L Concentration, c (g/kg) c2 c3 c1 30.0 50.0 70.0 15.0 25.0 35.0 10.0 17.0 25.0
Attention: Prepare only one batch of samples, either H, M or L. Refer to your lecturer for sample selection. Solution must be prepared in accurate concentration. In each sample preparation, weigh out accurately 10.0 g of solvent ( 12.0 ml) and put it into a 25 ml volumetric flask that can be tightly closed. Refer to OTR Operation Manual, Section 5.3 - 5.4.6 (pg. 5.1 - 5.4) to get data of R. Data Analysis (i) (ii) (iii) (iv) Record K value and the experimental conditions. Make a table of R and c values. Plot R/c versus c and determine Mn and B using equations (1) and (3). Discuss VPO method and results in your report.
References [1] [2] Operation Manual for VPO, page. 2-5 & 2-6 A. Rudin, The Elements of Polymer Science and Engineering, Academic Press, Chap. 3 (1982)
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(The values on the last column are those to be keyed into the computer) Membrane Osmometer Operation Procedure 1. Turn on the power supply of the machine. 2. LEDs (light) for Power and Heating are on, indicating the instrument is ready. (The Lab. Assistant might have turned the instrument on earlier, and left to stabilize before your measurement.) Operation procedure 1. Click on the File, go to new measurement, click on 090 molecular weight measurement. 2. Click start -- > 3. Key in the sample ID (e.g.: PS, H - your name). 4. Click on the blank area of Solution No 1, key in the concentration of the sample solution in the unit of g/100ml. Follow by the No. 2, No. 3, No. 4 & No. 5 (in increasing order of the concentration). 5. Click start -- > Make sure the liquid level in the suction bottle is low, otherwise pour the liquid into the waste solvent bottle. This is important to prevent the solvent back flow into the suction bulb. Baseline adjustment 1. 2. 3. 4. Click on the Select for Baseline adjustment. Press the suction bulb. Open the lid of inlet funnel Inject toluene into the inlet funnel with the syringe until the maximum level of the inlet funnel (marked as black line). (Reserve this syringe for transferring toluene only). 5. Close the lid. 6. Start the stop clock and wait for 2 minutes.
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Repeat the measurements for remaining sample solutions (No. 2, 3. 4 and 5) Every time you are measuring a new solution, first rinse the syringe (reserved for solution) with the new solution a few times, to ensure the contamination from the previous solution is at a minimum). Baseline correction Click on the Select for Baseline correction. Press the suction bulb. Open the lid of inlet funnel Inject toluene into the inlet funnel with the syringe until the maximum level of the inlet funnel (marked as black line). 5. Close the lid. 6. Start the stop clock and wait for 2 minutes. 7. Release the extension bar for the valve (anticlockwise direction) and let the toluene inside the inlet funnel flow till around 1cm from the bottom. (do not let the liquid flow empty, this will course the air suction into the machine). 8. Click on start -- > 9. Repeat step 1 to step 9 until the different between the two reading less than 3. 10. Click Finish 11. Click linear regression The computer software of the Osmometer would carry out the calculation and plot the graph for you. 1. 2. 3. 4.
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H H R1 C C
Y H R2
the activation energy for rotation of C-C bond depends on the properties of the substituted groups. An increase in size or polarity of the substituted groups can restrict the bond rotation, thus activation energy will increase. The frequency of bond rotation can be categorized by Arrhenius equation:
E a K = Xe RT
where X is assumed to have the same value as the frequency of torsional oscillation of C-C bond and Ea is activation energy of the bond rotation. Consequently, when the temperature is reduced, a value can be derived where the frequency of C-C bond rotation takes longer time than the experimental time period and rotation can no longer be detected. At this critical temperature, rotation is assumed to have stopped.
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will contain two big substitutions, P1 and P2 (if C-C bond is not part of the end group, beside the other substituted units). Activation energy for C-C bond rotation in polymers is usually in the order of 10-20 kcal mol-1 and depends on the size and polarity of the substituted groups. Therefore, the critical temperature (Tg) where the rotation can be observed to have stopped is in the range of -100oC to +200oC. At glass transition temperature, there is a unique transformation in polymer properties, from hard and relatively brittle at lower temperature to a rubbery state at high temperature. Beside an abrupt change in hardness and brittleness at glass transition, other properties such as the thermal expansion coefficient, heat transition, heat capacity, dielectric constant and deflection index also change. By observing the changes in these properties against temperature, Tg can be determined. In this experiment, Tg will be determined with dilatometry technique, i.e. by observing the change in height of the meniscus of the capillary tube / specific volume (thermal expansion coefficient) of the polymer over a certain temperature range. Procedure Fill a dilatometer, containing about 17 g poly(isobutyl methacrylate) with distilled water. Use long hypodermic tube until the water reaches about 1/3 of capillary tube. Grease oil can be used at the joints if necessary. Place dilatometer into the water bath set at 70oC to remove any air bubbles by rotating it. Then cool it down to room temperature. Immerse the dilatometer with the whole bulb in a water bath, equipped with temperature controller and heater. Take the value of the meniscus for every 3oC increase within the temperature range of 20-70oC. Temperature must be controlled to constant value (+ 1.0oC) for 5 minutes before the value of the meniscus is noted down. Data Analysis Plot the change in value of the meniscus against temperature. The point of inflexion in the curve gives the Tg value.
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Dt = D 1 e t
(1)
Where Dt refers to the deformation at time t and D the deformation after infinite time (Figure 1.)
Figure 1: Deformation of a Highly Elastic Material on Application of Stress A very important consequent of this theory is that for a particular material, whether it behaves as rubber or glass depends on the test time scale. For example, when the time taken to highly deform a material is extremely short, t << , the material will behave like a glass, but at longer test time, t >> , the material will behave like rubber. While t is influenced by the speed of the test, relaxation time is influenced by test temperature and obeys the normal exponential rate law
= Ae E RT
where E is related to the activation energy of a bond rotation. By combining equations (1) and (2), we will obtain
(2)
Dr D = 1 e [ t / Ae
E / RT
(3)
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As such, a sharp change from glassy to rubbery is expected to occur within a small range of temperature at a particular test speed. According to this theory, the actual Tg will depend on the speed of the test conducted. Tests at lower speed will show lower Tg. This experiment shows the significance of both parameters, time and temperature, in determining the elasticity of an elastic material. When an elastomeric ball is is dropped onto a hard surface it will rebound; the time of contact between the ball and the surface is very brief. The extent of rebounce depends on the temperature and can be shown by the rebound resilience defined as the ratio of regained energy in relation to the applied energy. If h0 is the initial height, and h is the rebounce height, the rebound resilience, is given by h/h0 and the energy loss for each rebounce isis (1 - h/h0). In this experiment, a plot of h/h0 against T will produce a curve which will go through a minimum at which the value T corresponds to the glass transition temperature Tg.
Experimental Procedure
1) Two samples, a natural rubber (NR) ball and a butyl rubber ball, are used in this experiment. At room temperature, the NR ball will rebound higher than the butyl rubber ball. 2) The experiment will be conducted at temperatures from -80oC to +60oC. Temperatures below 0 oC is obtained by mixing liquid N2 with water. Use a Dewar flask to prepare a sub-zero environment. Immersed the rubber balls, together with the metal tong, in the flask for 3 minutes. Set up a meter ruler to read vertically upwards. Using the tong, hold the rubber ball at a height of 60 cm (ho), then relaese it to drop onto a hard surface of your work-bench. Note the height of the rebounce (h). Take two readings. Repeat the process with the other sample. Continue the experiment for other temperatures.
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Tg = Tg' +
(4)
where a = t/t. here, Tg is obtained from a technique of known test time t, while Tg' corresponds to t'. The values of t for different test is given in the Table 1 below: Table 1 : Test Time (t) Test Thermal expansion Mechanical Loss Rebound Resilience Dielectric loss Broadline NMR t(s) 104 1 - 104 10-5 10-2 - 10-8 10-4 - 10-5
Tg = Tg' +
100 = Tg' +
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S = k log W
(1)
The idea that polymer, with its high molecular weight, should display elasticity, obviously, is not totally true because there are actually four basic criteria for the elasticity of rubber: (i) The material must be made up of long chain molecules which can rotate freely,
(ii) Has weak intra-molecular atrractive forces (iii) The molecules are joined or crosslinked along the chains, and (iv) The polymer is above its glass transition temperature Tg Unvulcanised rubber does not fulfil these criteria because the polymer chains are not crosslinked. However, apparent crosslinks exist from the entanglement of the polymer chains. The elasticity of NR can be improved by chemically introducing the crosslinks through a process known as vulcanisation or curing. Although rubber does not behave like solid, gas or liquid, part of its behaviour can be understood from the analogy of the properties of a perfect gas. Pressure exerted by gas on the wall of a vessel is caused by the continuous and random bombardment of the gas molecules; tension on an extended rubber is caused by the random thermal movement of segments of the polymer chain. Gas molecules are inclined towards a most probable distribution in space. Similarly, the segments of the polymer chains are inclined towards the most probable, randomly coiled condition.
We can also produce an equation for rubber, similar to the ideal gas equation, P = nRT/V. the equation for the situation is,
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F=
dRT 2 Mc
(2)
where F is the tensional force (i.e. the force per cross-sectional area of the unextended rubber sample, kg cm-2), d is the density of rubber (g cm-3), R the gas constant, T the absolute temperature (K), Mc is the molecular weight between crosslinks, and the ratio of the extended length to its original. Just as no gas behaves as ideal gas, similarly, rubber will display a deviation from its ideal behaviour, such that the equation is modified to fit actual observation,
F=
gdRT M 2 1 2 c Mc M
(3)
where g is a correction factor for the additional (apparent) crosslinks caused by the physical entanglement of polymer chains, M the molecular weight of the elastomer, and the expression (1 - 2Mc/M) is a modification which takes into consideration the existance of free ends in a 3-dimensional network. In this experiment, the degree of vulcanisation, Mc as determined by the Mooney-Rivlin equation (3) will only be true at low extension ( < 1.5). Experimental Procedure Mark two positions, a distance of 5 cm (lo) on the rubber sample. Grip the sample with 2 clips; make sure the markings are visible. Hang the sample as shown in Figure 1. Weigh the container which will be attached to the lower clip. Measure the distance between the markings. Add weights successively and measure the corresponding lengths (l) of the sample until it it is extended to about 25 cm. Remove the weight successively and again measure the corresponding length of the sample. Determine w, the weight (g) per cm of the sample. See equation (5)
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L /( 2 ) = l + S1
(4)
where l and S are constants that can be determined from the plot L/( - -2) against -1. Mc, can be calculated from the equation Mc = W'RT/I (g/mol) where W' = R = weight of sample/lo (g/cm) 84.7 kg.cm.mol-1.K-1 (5)
PART B : Swelling Method Raw rubber (e.g. latex and unvulcanised rubber) can be perfectly miscible with good solvents such as toluene and chloroform; but once vulcanised, it becomes almost insoluble. It cannot be dispersed by solvent but will undergo swelling; the amount of solvent absorbed depends on the extent of crosslinking. This is almost similar to the solubility of a polymer. However, in swelling the penetration of solvent into the polymer network has an opposing effect to the elastic shrinkage of the network. At equilibrium, these two effects are in balance. The equilibrium degree of swelling can be understood from the combination of the theories of solution and elasticity of rubber. The equations enable the calculation of Mc, from the degree of swelling of a rubber. Experimental Procedure TWO steps are involved. (1) Determination of density of rubber Cut the rubber sample into small pieces ( 5 mm), and place them in a 100 ml beaker. Pour into it 25 ml of glycerol. Using a burette, gradually add methanol into the beaker, with occassional shaking, until the rubber pieces remain suspended in the methanol/glyecerol mixture. At this instance, the densities of the rubber and the solution mixture are the same. Detremine the density of the mixture using a SG bottle. (2) Determination of the swelling of the rubber sample Cut about 3 cm of the rubber sample and accurately determine its weight. Place the sample in a conical flask containing 25 ml toluene. Stopper the flask and place it in a dark corner of a cupboard for at least 12 hours. Take the rubber out and place it on a wire mesh for 5 seconds. Transfer the rubber to a weighing bottle of known weight, close it, and determine the weight of the rubber.
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Wg - W ] d Qm = W [ ] d [
(6)
where Wg is the weight of swollen rubber, W the initial weight of rubber, d' the density of toluene (0.867 g.ml-1) and d the density of rubber [from (1)]. The volume fraction of rubber in the swollen sample is,
V2 =
1 1 + Qm
(7)
The molecular weight Mc can then be calculated from the following equation,
dV0V21 3 Mc = ln (1 V2 ) + V2 + V22
(8)
where Vo is the molar volume of toluene (mol. wt / density), and the interactive constant between natural rubber and toluene (= 0.42). Determination of the density of rubber: 1. Cut a portion of the rubber sample (~10 cm) and determine its ACCURATE weight. 2. Fill a 5 ml. measuring cylinder with distilled water to its 3.00 0.05 ml. 3. Cut the rubber into smaller pieces and put them into the measuring cylinder. [Make sure there are no AIR BUBBLES on the rubber samples]. 4. Accurately read the new water level in the flask. 5. Determine the volume (V) of the rubber. 6. Calculate thedensity of the rubber,
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