Polymers Flashcards

1
Q

What are the three categories of polymers?

A
  • natural (proteins, polysaccharides, resins/gums)
  • semi-synthetic
  • synthetic (plastics, elastomers, rubber)
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2
Q

Define polymer chemically

What are four potential structures?

A

a long chain molecule (MW of several thousand/million atomic units) constructed from many monomers (like structured molecules) covalently bonded together in any conceivable pattern

linear
branched
cross-linked
colloidal

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3
Q

Define dimer and trimer

A

dimer - bonded to one of self (O-O)
trimer - bonded to two of self (O-O-O)

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4
Q

What are the two polymer types in terms of diversity?

A

homopolymers - all the same monomer (doesn’t have to be linear)

co-polymers - made up of different monomers

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5
Q

What two things can monomers be?

Give examples of these

A

small (PVC)
complex (nylon)

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6
Q

What are the different types of chemical linkages?

What does this depend on?

What does this usually require?

A
  • linear or branched structures
  • depends on monomer functionality
  • sometimes they’ll self assemble but most of the time they need to be initiated
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7
Q

How can monomers perpetuate chain growth?

A
  • monomers may have complimentary reactivity (react with self to form dimer etc) or react with another different monomer to perpetuate chain growth
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8
Q

Where are dendrimers used?

How are these helpful?

A
  • used in drug delivery
  • if can identify polymer then can find out where drug was manufactured
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9
Q

How do polymers form?

How do polymers end?

What is an exception to this?

A
  • by chains reacting and forming bonds
  • the end cannot have dangling half bond - must be something there
  • polymers end by something called end groups (important for polymer analysis)
  • no end groups in rings
  • very rare as most industrial processes will have rings
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10
Q

What does ratio of end groups to in-chain groups allow?

What does the uniqueness of end group mean?

A
  • allows for measuring of polymer length
  • nature of end group is unique
  • this allows the method of synthesis to be identified
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11
Q

What type of end groups allow for further modification and of what?

A
  • reactive end groups allow further modification to control properties or add additional functionality
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12
Q

What are the three main types of polymer when classed by bulk properties?

Describe the first two in terms of:
- what happens when heated
- what happens after being heated?
- flexibility (why?)
- what is required for them to be produced
- examples of them

Describe the third one in terms of:
- what type it can be
- its two properties
- examples

A

thermoset:
- burns when heated
- irreversibly hardened once shaped
- generally inflexible (crosslinking in curing process means chains linked together inhibit molecular motion)
- requires curing (chemical process) in order to produce them (also requires curing agent)
- e.g. polyurethanes, epoxy resin (superglue), silicones

thermoplastics
- melts when heated
- can be remelted and reshaped
- generally more flexible (disordered regions facilitate molecular motion)
- no chemical curing required
- e.g. polystyrene, nylon, polycarbonate

elastomer
- can be thermoset or thermoplastic
- viscoelastic so has viscosity (can flow) and elasticity (returns to original shape)
- e.g. rubbers (natural, butyl, silicone)

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13
Q

Describe the two types of polyethylene polymers in terms of density:
- examples
- density
- branching
- crystalline content
- transparency
- hardness
- gas permeability

A

high density polyethylene (HDPE)
- containers/lids, food bottles, petrol tank, motor oil bottles, crates, pipers
- higher density than LDPE
- very low or no branching
- high crystalline content - 70-90 % (very well aligned)
- less transparent than LDPE
- stiffer and harder than LDPE
- less gas permeable than LDPE

low density polyethylene (LDPE)
- film/sheet packaging, toys, squeeze bottles, plastic bags, wire and cable coatings
- lower density than HDPE
- highly branched (around 60 branch points per 1000 carbon atoms)
- low crystalline content - 40-60 % (far less aligned)
- more transparent than HDPE
- not as stiff and hard as HDPE - forms good films
- more gas permeable than HDPE

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14
Q

How are physical properties of polymer determined?

How are they controlled?

What does measuring properties and understanding of chemistry allow for?

A
  • how adjacent chains interact and are linked
  • supramolecular interactions (H bonds, van der Waals interactions etc)
  • covalent interactions (cross-linking of chains etc.)
  • controlled by underlying chemistry
  • allows us to identify and compare polymeric trace evidence types (compare known and unknown)
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15
Q

Define crystallinity?

what is the scale used to measure crystallinity?

what 7 physical properties does crystallinity affect?

what does measuring crystallinity allow for? in what ways is this done?

A
  • the regions of atomic ordering where intramolecular folding/stacking of adjacent chains occur
  • degree of crystallinity:
  • 0 = completely amorphous (not aligned)
  • 1 = completely crystalline (aligned)
  • impact resistance
  • Young’s Modulus
  • tensile strength
  • stiffness
  • crease
  • thermal behaviour
  • transparency
  • allows for identification of polymer and comparison between samples
  • directly or indirectly
  • destructively (cheaper and easier) - depending on availability of evidence type as it is useful if can and do not have to delve into more complex non-destructive testing
  • non-destructive testing (optical/spectroscopic methods)
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16
Q

define tensile strength

what is the correlation between tensile strength, polymer chain length and crosslinking (why)

A
  • how much something will stretch before it breaks (elongation stress)
  • for polymers, tensile strength increases with polymer chain length and crosslinking (more interaction between chains)
17
Q

How is tensile strength measured?

How is this method normalised/standardised?

A
  • take a sample and stretch (this destructive method is cheaper and easier than non-destructive method)
  • need to normalise this so we can standardise for sample size
  • it is easier to stretch smaller things than large things (more matter to move = more force required)
  • take into account sample length and sample cross section
18
Q

What are stretch and force termed in solids?

How are these calculated?

How are these equations standardised/normalised?

Positive/negative sign? and why?

A
  • stretch is called strain
  • force is called stress
  • strain = I/L
  • strain = distance stretched/length
  • this is a fractional change so is independent of length
  • stress = F/A
  • stress = force/area
  • independent of sample size
  • minus sign as force in opposite direction to applied force - if you in one direction (x) then the spring pulls back in the opposite way
19
Q

How is young modulus calculated?

What does it describe?

What unit is it usually given in?

A
  • E = strain/stress
  • describes how stiff a solid is
  • so large they are usually reported in GPa
20
Q

Define Hooke’s Law

A

for a spring, F = -kx
where k = force/spring constant

21
Q

Describe the behaviour of a thermoplastic polymer being stretched?

A

ELASTIC deformation region:
- necking - where bits on end are quite bulky but things in middle start to stretch out
- this is shown as turning point on plot

PLASTIC deformation region:
- keep stretching beyond that - we get drawing
- much less disordered now (more ordered)
- when fully drawn = polymer breaks = fracture

22
Q

How can young’s moduli be useful in trace evidence?

What does this look like for three types of polymers

A
  • measuring young’s moduli and plotting stress (y) vs strain (x) plots allows for identification of polymer and comparison between polymeric samples

thermoset - almost immediately upright until fractures
thermoplastic - up then down then across
elastomer - almost immediately directly proportional

23
Q

What are the phase transitions for amorphous and Pseudocrystalline materials as increase temperature?

What is glass transition temp higher for?

A

amorphous:
- glass
- reach glass transition temp
- rubber
- gum
- liquid

Pseudocrystalline
- crystalline
- reach glass transition temp
- flexible thermoplastic
- reach melting temp
- liquid

  • glass transition temp higher for Pseduocrystalline
24
Q

define glass transition temperature

how is this useful in forensics?

A
  • not the melting point but a temp at which the tension in the polymer backbone lessens sufficiently to impart flexibility, but not flow
  • it is unique to material and therefore identifiable region of a material that allows us to identify it and see more information
25
Q

What can measuring thermal properties of polymer allow for?

What can this be combined with?

A
  • allows identification of polymer and comparison between polymeric samples
  • can be combined with optical or spectroscopic techniques for even greater level of information
26
Q

What does phase at RT dictate?

What is it if above Tg and Tm, between them, or below both?

A
  • generally
  • phase at RT dictates applications
  • above Tg and Tm = viscous liquid
  • above Tg and below Tm = rubbery solid (may still flow)
  • below Tg and Tm = solid
27
Q

Describe the uses of:
polyisoprene
Polyvinylidenechloride
polytetrafluoroethylene

A

polyisoprene:
- not very useful as liquid at RT
- can be cross-linked to make extremely useful materials

Polyvinylidenechloride :
- commonly used to coat other plastics
- soft and transparent
- BUT very chemical resistant

polytetrafluoroethylene
- TEFLON
- forms a strong hard coating on frying pans amongst other applications