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Micro Structures in Polymers Chapter 3

Professor Joe Greene CSU, CHICO

MFGT 041

September 20, 1999

Chapter 3 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

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.
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 .

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



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

Gel Permeation Chromatography

GPC Used to measure Molecular Weights
form of size-exclusion chromatography smallest molecules pass through bead pores, resulting in a relatively long flow path largest molecules flow around beads, resulting in a relatively short flow path chromatogram obtained shows intensity vs. elution volume correct pore sizes and solvent critical

Gel Permeation Chromatography

M N i M i N1 M 1 N 2 M 2 N 3 M 3 ... n

Number Average Molecular Weight, Mn


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

Number Average Molecular Weight. Figure 3.2

The data yields a nonsymmetrical curve (common) The curve is skewed with a tail towards the high MW The Mn is determined experimentally by analyzing the number of end groups (which permit the determination of the number of chains) The number of repeating units, n, can be found by the ratio of the Mn and the molecualr weight of the repeating unit, M0, for example for polyethylene, M0 = 28 g/mole The number of repeating units, n, is often called the Mn degree of polymerization, DP. n DP relates the amount of M0 11 monomer that has been converted to polymer.

Molecular Weight

Weight Average Molecular Weight, Mw

2 N1 M 12 N 2 M 2 N 3 M 32 ... Mw N i M i N1 M 1 N 2 M 2 N 3 M 3 ... 2 N M i i

Weight Average Molecular Weight, Mw

Favors large molecules versus small ones Useful for understanding polymer properties that relate to the weight of the polymer, e.g., penetration through a membrane or light scattering. Example,
Same data as before would give a higher value for the Molecular Weight. Or, Mw = 420,000 g/mole


3 3 N1 M 13 N 2 M 2 N3M 3 ... Mz 2 2 2 2 N M N M N M N M i i 1 1 2 2 3 3 ...

3 N M i i

Z- Average Molecular Weight

Emphasizes large molecules even more than Mw Useful for some calculations involving mechanical properties. Method uses a centrifuge to separate the polymer


Molecular Weight Distribution

Molecular Weight Distribution represents the frequency of the polymer lengths The frequency can be Narrow or Broad, Fig 3.3 Narrow distribution represents polymers of about the same length. Broad distribution represents polymers with varying lengths MW distribution is controlled by the conditions during polymerization MW distributions can be symmetrical or skewed. 14

Physical and Mechanical Property Implications of MW and MWD

Higher MW increases
Tensile Strength, impact toughness, creep resistance, and melting temperature.

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.

Higher MW increases tensile strength

Physical and Mechanical Property Implications of MW and MWD

Resistance to an applied load pulling in opposite directions Tension forces cause the polymers to align and reduce the number of entanglements. If the polymer has many entanglements, the force would be greater.

Broader MW Distribution decreases tensile strength

Broad MW distribution represents polymer with many shorter molecules which are not as entangled and slide easily.

Higher MW increases impact strength

Impact toughness or impact strength are increased with longer polymer chains because the energy is transmitted down chain.

Broader MW Distribution decreases impact strength

Shorter chains do not transmit as much energy during impact

Thermal Property Implications of MW & MWD

Higher MW increases Melting Point
Melting point is a measure of the amount of energy necessary to have molecules slide freely past one another. If the polymer has many entanglements, the energy required would be greater. Low molecular weights reduce melting point and increase ease of processing.

Broader MW Distribution decreases Melting Point

Broad MW distribution represents polymer with many shorter molecules which are not as entangled and melt sooner. Broad MW distribution yields an easier processed polymer * Decomposition

Example of High Molecular Weight

Ultra High Molecular Weight Polyethylene (UHWMPE)
Modifying the MWD of Polyethylene yields a polymer with
Extremely long polymer chains with narrow distribution Excellent strength Excellent toughness and high melting point.

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

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


Melt Index and Viscosity

Melt index is similar to viscosity Viscosity is a measure of the materials resistance to flow.
Viscosity is measured at several temperatures and shear rates Melt index is measured at one temperature and one weight.

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

Melt Index and Molecular Weight

Melt index is related closely with average molecular weight High melt index = high flow = small chain lengths = low Mn Low melt index = slow flow = long chain lengths = high Mn Table 3.1 Melt Index and Average Molecular Weight Mn Melt Index* (g/10min) 100,000 10.00 150,000 0.30 250,000 0.05
* Note: PS at T= 200C and mass= 5.0Kg

States of Thermoplastic Polymers

Amorphous- Molecular structure is incapable of forming regular order (crystallizing) with molecules or portions of molecules regularly stacked in crystal-like fashion. A - morphous (with-out shape) Molecular arrangement is randomly twisted, kinked, and coiled


Amorphous Materials
PVC Amorphous PS Amorphous Acrylics Amorphous ABS Amorphous Polycarbonate Amorphous Phenoxy Amorphous PPO Amorphous SAN Amorphous Polyacrylates Amorphous


States of Thermoplastic Polymers

Crystalline- Molecular structure forms regular order (crystals) with molecules or portions of molecules regularly stacked in crystal-like fashion. Very high crystallinity is rarely achieved in bulk polymers Most crystalline polymers are semi-crystalline because regions are crystalline and regions are amorphous Molecular arrangement is arranged in a ordered state


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


Factors Affecting Crystallinity

Cooling Rate from mold temperatures Barrel temperatures Injection Pressures Drawing rate and fiber spinning: Manufacturing of thermoplastic fibers causes Crystallinity Application of tensile stress for crystallization of rubber

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

Melt Rubbery

Polymer Form as a function of temperature

Glassy: Solid-like form, rigid, and hard


Polymer Form 27

Glass Transition Temperature, Tg

Glass Transition Temperature, Tg: The temperature by which:
Below the temperature the material is in an immobile (rigid) configuration Above the temperature the material is in a mobile (flexible) configuration

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.

Glass Transition Temperature, Tg

Glass Transition Temperature, Tg: Defined as
the temperature wherein a significant the loss of modulus (or stiffness) occurs the temperature at which significant loss of volume occurs
Modulus (Pa) or (psi)


-50C 50C 100C 150C 200C 250C




-50C 50C 100C 150C 200C 250C

Crystalline Polymers: Tm

Tm: Melting Temperature



Rubbery Glassy Polymer Form

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

Modulus (Pa) or (psi)

High Crystallinity Medium Crystallinity Low Crystallinity

-50C 50C 100C 150C 200C 250C


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

-50C 50C 100C 150C 200C



Thermal Properties
Table 3.2 Thermal Properties of Selected Plastics