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MFGT 041
Chapter 3 Objectives
Objectives
Polymer length, molecular weight, molecular weight distribution (MWD) Physical and mechanical property implications of molecular weight and MWD Melt Index Amorphous and crystalline structures in polymers Thermal transitions in plastics (thermoplastics and thermosets Steric (shape) effects
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Polymer Length
Polymer Length
Polymer notation represents the repeating group
Example, -[A]-n where A is the repeating monomer and n represents the number of repeating units.
Molecular Weight
Way to measure the average chain length of the polymer Defined as sum of the atomic weights of each of the atoms in the molecule.
Example,
Water (H2O) is 2 H (1g) and one O (16g) = 2*(1) + 1*(16)= 18g/mole Methane CH4 is 1 C (12g) and 4 H (1g)= 1*(12) + 4 *(1) = 16g/mole 3 Polyethylene -(C2H4)-1000 = 2 C (12g) + 4H (1g) = 28g/mole * 1000 =
Molecular Weight
Average Molecular Weight
Polymers are made up of many molecular weights or a distribution of chain lengths.
The polymer is comprised of a bag of worms of the same repeating unit, ethylene (C2H4) with different lengths; some longer than others. Example,
Polyethylene -(C2H4)-1000 has some chains (worms) with 1001 repeating ethylene units, some with 1010 ethylene units, some with 999 repeating units, and some with 990 repeating units. The average number of repeating units or chain length is 1000 repeating ethylene units for a molecular weight of 28*1000 or 28,000 g/mole .
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Molecular Weight
Average Molecular Weight
Distribution of values is useful statistical way to characterize polymers.
For example,
Value could be the heights of students in a room. Distribution is determined by counting the number of students in the class of each height. The distribution can be visualized by plotting the number of students on the x-axis and the various heights on the y-axis.
Histogram of Heights of Students
25 20 15 10 5 0 60 70 Height, inches 80
Frequency
Series1
Molecular Weight
Molecular Weight Distribution
Count the number of molecules of each molecular weight The molecular weights are counted in values or groups that have similar lengths, e.g., between 100,000 and 110,000 For example,
Group the heights of students between 65 and 70 inches in one group, 70 to 75 inches in another group, 75 and 80 inches in another group.
The groups are on the x-axis and the frequency on the y-axis. The counting cells are rectangles with the width the spread of the cells and the height is the frequency or number of molecules Figure 3.1 A curve is drawn representing the overall shape of the plot by connecting the tops of each of the cells at their midpoints. 6 The curve is called the Molecular Weight Distribution (MWD)
Molecular Weight
Average Molecular Weight
Determined by summing the weights of all of the chains and then dividing by the total number of chains. Average molecular weight is an important method of characterizing polymers. 3 ways to represent Average molecular weight
Number average molecular weight Weight average molecular weight Z-average molecular weight
M N i M i N1 M 1 N 2 M 2 N 3 M 3 ... n
N1 N 2 N 3 ...
where Mi is the molecular weight of that species (on the x-axis) where Ni is the number of molecules of a particular molecular species I (on the y-axis). Number Average Molecular Weight gives the same weight to all polymer lengths, long and short. Example, What is the molecular weight of a polymer sample in which the
polymers molecules are divided into 5 categories. Group Frequency N i M i N1 M 1 N 2 M 2 N 3 M 3 ... M n 50,000 1 N1 N 2 N 3 ... Ni 100,000 4 1(50K ) 4(100K ) 5(200K ) 3(500K ) 1(700K ) Mn 200,000 5 (1 4 5 3 1) M n 260,000 500,000 3 10 700,000 1
Molecular Weight
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3 N M i i
Emphasizes large molecules even more than Mw Useful for some calculations involving mechanical properties. Method uses a centrifuge to separate the polymer
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Due to entanglement, which is wrapping of polymer chains around each other. Higher MW implies higher entanglement which yields higher mechanical properties. Entanglement results in similar forces as secondary or hydrogen bonding, which require lower energy to break than crosslinks.
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Material works well in injection molding (though high melt T) Does not work well in extrusion or blow molding, which require high melt strength. Melt temperature range is narrow and tough to process. Properties improved if lower MW polyethylene
Acts as a low-melting lubricant Provides bimodal distributions, Figure 3.5 Provides a hybrid material with hybrid properties
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Melt Index
Melt index test measure the ease of flow for material Procedure (Figure 3.6)
Heat cylinder to desired temperature (melt temp) Add plastic pellets to cylinder and pack with rod Add test weight or mass to end of rod (5kg) Wait for plastic extrudate to flow at constant rate Start stop watch (10 minute duration) Record amount of resin flowing on pan during time limit Repeat as necessary at different temperatures and weights
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High melt index = high flow = low viscosity Low melt index = slow flow = high viscosity Example, (flow in 10 minutes)
Polymer Temp Mass HDPE 190C 10kg Nylon 235C 1.0kg PS 200C 5.0Kg
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Amorphous Materials
PVC Amorphous PS Amorphous Acrylics Amorphous ABS Amorphous Polycarbonate Amorphous Phenoxy Amorphous PPO Amorphous SAN Amorphous Polyacrylates Amorphous
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Crystalline Materials
LDPE HDPE PP PET PBT Polyamides PMO PEEK PPS PTFE LCP (Kevlar) Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline Crystalline
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Form of Polymers
Thermoplastic Material: A
material that is solid, that possesses significant elasticity at room temperature and turns into a viscous liquid-like material at some higher temperature. The process is reversible Temp
Tm
Melt Rubbery
Tg
Glassy
Polymer Form 27
Transition is called Glass Transition because the properties below it are similar to ordinary glass. Transition range is not one temperature but a range over a relatively narrow range (10 degrees). Tg is not precisely measured, but is a very important 28 characteristic.
Vol.
Tg
-50C 50C 100C 150C 200C 250C
Tg
Temperature
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Tg
Temperature
Crystalline Polymers: Tm
Melt
Tm
Temp
Tg
T > Tm, The order of the molecules is random (amorphous) T < Tm >Tg, Crystallization begins at various nuclei and the order
of the molecules is a mixture of crystals and random polymers (amorphous). Crystallization continues as T drops until maximum crystallinity is achieved. The amorphous regions are rubbery and dont contribute to the stiffness. The crystalline regions are unaffected by temperature and are glassy and rigid.
30 T < Tg, The amorphous regions gain stiffness and become glassy
Crystalline Polymers Tg
Tg: Affected by Crystallinity level
High Crystallinity Level = high Tg Low Crystallinity Level = low Tg
Tg
-50C 50C 100C 150C 200C 250C
Temperature
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Temperature Effects on Specific Volume T > Tm, The amorphous polymers volume decreases linearly with T.
T < Tm >Tg, As crystals form the volume drops since the crystals are significantly denser than the amorphous material. T < Tg, the amorphous regions contracts linearly and causes a change in slope
Specific Volume
Tg
-50C 50C 100C 150C 200C
Tg
250C
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Temperature
Thermal Properties
Table 3.2 Thermal Properties of Selected Plastics
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