Topics on Materials and Manufacture

Topic 1: Atomic Structure and Bonding

Topic 2: Carbon Steels and Alloy Steels
Topic 3: Heat Treatment of Carbon Steels

Topic 4: Polymer Materials

Topic 5: Polymer Matrix Composites (PMCs)
Topic 6: Thermoplastics Manufacturing
Topic 7: Polymer Matrix Composites (PMCs) Manufacturing
Topic 8: Conventional Machining
Topic 9: Non-Conventional Machining
Topic 10: Joining Processes
Topic 11: Rapid Prototyping and Additive Manufacturing
Topic 12: Ceramic Materials
Z
 Materials Classification
Metal Alloys Polymers Ceramics Composites

Polymers

Synthetic Polymers Natural Polymers

Wood Fibre Resin

Plastics Elastomers Adhesives

Synthetic
Fibres
Thermoplastics Thermosets
Z
 Polymerisation

Addition Polymerisation Condensation Polymerisation

One monomer with More than one monomer Two monomers with two
double bond with double bond functional groups at both ends

Homo-polymers Co-polymers Condensation polymers

Polymer Blends and Alloys Filled Polymers

(Homo-polymers + Co-polymers + (Polymer + Additives)
Condensation polymers)

Methods of Producing Different Polymer Materials

 Polymerisation

Addition Polymerisation Condensation Polymerisation

One monomer with More than one monomer Two monomers with two
double bond with double bond functional groups at both ends

Homo-polymers Co-polymers Condensation polymers

Polymer Blends and Alloys Filled Polymers

(Homo-polymers + Co-polymers + (Polymer + Additives)
Condensation polymers)

Methods of Producing Different Polymer Materials

 CH3-CH3

Ethane

CH2= CH2

Ethylene

CH= CH

Acetylene

=Carbon Atom =Hydrogen Atom

Illustration of Covalent Bonding and Saturation Z

Electron Dot Structure of Ethylene
 CH2= CH2 + CH2= CH2 + CH2= CH2+ CH2= CH2

T P Catalyst

– CH2–CH2 – CH2–CH2–CH2 – CH2–CH2–CH2 –

T P
n CH2= CH2 ( CH2–CH2 ) n
Catalyst

Addition Polymerization of Polyethylene Z

 Materials with Different Molecular Chain Lengths

( CH2 CH2 ) n HMW Polyethylene

Polyethylene
Generic Formula
Solid Wax

Bitumen
Liquid Wax
Diesel

Petrol

Propane

Ethane

Methane
Molecular
Weight
Z
 Materials with Different Molecular Chain Lengths

( CH2 CH2 ) n HMW Polyethylene

Polyethylene
Generic Formula
Solid Wax

Bitumen
Liquid Wax
Diesel

Petrol

Propane

Ethane

Methane
Molecular
Weight
Z
 Addition Polymerization
1. In presence of an appropriate combination of heat, pressure, and catalysts, the
double bond between the carbon atoms is broken and replaced with a single
covalent bond.
2. The ends of the monomer are now free radicals; each carbon atom has an
unpaired electron that it may share with other free radicals.
3. Addition polymerisation occurs because the original monomer contains a
double covalent bond between the carbon atoms.
4. The double bond is an unsaturated bond. After changing to a single bond, the
carbon atoms are still joined, but they become active; other repeat units can be
added to produce the polymer chain.
5. In ethylene there are two locations (each carbon atoms) at which molecules
can be attached. Thus, ethylene is bi-functional, and only chains form.
6. The functionality is the number of sites at which new molecules can be
attached to the repeat unit of the polymer.
7. If there are three or more sites at which molecules can be attached, a three-
dimensional network forms.
 Addition Polymerization Monomers and Polymers
Monomer Polymer Name

CH2= CH ( CH2- CH) n

Polyethylene
H H
CH2= CH ( CH2- CH ) n
Polypropylene
CH3 CH3
CH2= CH ( CH2- CH ) n Polyvinyl Chloride
Cl Cl

CH2= CH ( CH2- CH ) n
Poly Styrene
C 6 H5 C 6 H5

CF2= CF2 ( CF2- CF2 ) n Polytetrafluoroethylene

CO2CH3 CO2CH3
CH2= C ( CH2- C ) n Polymethyl methacrylate
CH3 CH3 Z
 Addition Polymerization Monomers and Polymers
Monomer Polymer Name

CH2= CH ( CH2- CH) n

Polyethylene
H H
CH2= CH ( CH2- CH ) n
Polypropylene
CH3 CH3
CH2= CH ( CH2- CH ) n Polyvinyl Chloride
Cl Cl

CH2= CH ( CH2- CH ) n
Poly Styrene
C 6 H5 C 6 H5

CF2= CF2 ( CF2- CF2 ) n Polytetrafluoroethylene

CO2CH3 CO2CH3
CH2= C ( CH2- C ) n Polymethyl methacrylate
CH3 CH3 Z
Number Average and Weigh Average Molecular Weight

Number average molecular weight is a way of determining the molecular weight

of a polymer. Polymer molecules come in different sizes, so the average molecular
weight will depend on the method of averaging. The number average molecular
weight is the common average of the molecular weights of the individual polymers.
It is determined by measuring the molecular weight of n polymer molecules,
summing the weights and dividing by N.

Weight average molecular weight is a is calculated by the following equation,

where Ni is the number of molecules of molecular weight Mi.

Z
 Degree of Polymerisation and Molecular
Weight Distribution
Degree of Polymerisation is a measure of the number of repeating unit in a polymer. It
can be calculated by the number average molecular weight divided by the molecular weight
of the monomer.

Number Average Molecular Weight

Degree of Polymerization=
Molecular Weight of Repeating Unit

Polydispersity Index (PDI) is a measure of the distribution of molecular weights in a

given polymer sample. The PDI is defined as the weight average molecular weight divided
by the number average molecular weight. It indicates the distribution of individual
molecular weights in a batch of polymers. The PDI has a value always greater than 1 but as
the polymer chains approach uniform chain length, the PDI approaches 1.
___

Mw
PDI  ___

Mn
Z
 Determination of Degree of Polymerisation/Molecular Weight
/Molecular Weight Distribution of Polymers

___
_
Mn 
i
NM i i
_
Mw 
 NM
i i i
2

PDI 
Mw
N i i NM
i i i
___

Mn
Number Average Molecular Weight
Degree of Polymerization=
Molecular Weight of Repeating Unit

Assume that the molecular weight distributions of two grades of HDPE are
as follows.

Number of Molecules 25 50 25

Molecular Weight of HDPE A 1000 10000 19000

Molecular Weight of HDPE B 8000 10000 12000

Z
 Determination of Number Average and Weight
Average Molecular Weights HDPE A

_
Mn 
 NM
i i i

N i i

25  1000  50  10000  25  19000 1000000

   10000( g / mol )
25  50  25 100

_
Mw 
 NM i i i
2

NM i i i

25  10002  50  100002  25  190002 14050  106

   14050( g / mol )
25  1000  50  10000  25  19000 1000000

Z
 Determination of Degree of Polymerisation and
Molecular Weight Distribution of HDPE A

CH2= CH2

Molecular weight of monomer ethylene=2 × 12+4 × 1=28 (g/mol)

Number Average Molecular Weight

Degree of Polymerization=
Molecular Weight of Repeating Unit

10000
  357
28
Polydispersity Index
_
Mw 14050
PDI  _
  1.405
Mn 10000

Z
 Determination of Number Average and Weight
Average Molecular Weights HDPE B
_
Mn 
i
NM i i

N i i

25  8000  50  10000  25  12000 1000000

   10000( g / mol )
25  50  25 100

Mw
_

 NM i i i
2

NM i i i

25  80002  50  100002  25  120002 1.02  1010

   10200( g / mol )
25  8000  50  10000  25  12000 10 6

Z
 Determination of Degree of Polymerisation and
Molecular Weight Distribution of HDPE B

CH2= CH2

Molar mass of C = 12 g/mol Molar mass of H=1 g/mol

Monocular weight of monomer ethylene=2 × 12+4 × 1=28

(g/mol)
Number Average Molecular Weight
Degree of Polymerization=
Molecular Weight of Repeating Unit

10000
  357
28
_
Mw 10200
PDI  _
  1.02
Mn 10000
Z
 Comparison Between HDPE A and HDPE B
___
_
Mn 

i
NM i i
_
Mw 
 NM i i i
2

PDI 
Mw
N i i NM i i i
___

Mn
Number Average Molecular Weight
Degree of Polymerization=
Molecular Weight of Repeating Unit

Number of Molecules 25 50 25
Molecular Weight of HDPE A 1000 10000 19000

Molecular Weight of HDPE B 8000 10000 12000

Polymer Number average Weight average Degree of Polydispersity

molecular weight molecular weight Polymerisation Index (PDI)
HDPE A 10000 14500 357 1.45

HDPE B 10000 10200 357 1.02

Z
Melt Flow Index (MFI) Tester
Z
 Melt Flow Index (MFI)
1. MFI is a measure of the ease of flow of the melt of a thermoplastic.
2. It is defined as the weight of polymer in grams flowing in 10 minutes through a
capillary of specific diameter and length by a pressure applied via prescribed
alternative gravimetric weights.
3. The method is given in ASTM D1238 and ISO 1133.
4. The melt flow rate is an indirect measure of molecular weight, high melt flow
rate corresponding to low molecular weight.
5. The melt flow rate is a measure of the ability of the material's melt to flow
under pressure.
6. The melt flow rate is inversely proportional to the viscosity of the melt at the
conditions of the test, though it should be born in mind that the viscosity for
any such material depends on the applied force.
7. Ratios between two melt flow rate values for one material at different
gravimetric weights is often used as a measure for the broadness of the
molecular weight distribution.
8. Melt flow rate is very commonly used for many polymers.
9. Polyethylene is measured at 190°C and 2.16 Kg weight.
Z
 Copolymerisation
1. In addition to making changes by substitution in the basic repeating unit (PE,
PVC PS), it is possible to change the chemical composition and hence the
structure, and the properties of a polymer be mixing different types of basic
repeating unit within the chain of a polymer. This is done by a process co-
polymerisation;
2. The repeating units can be arranged in four different ways called random,
alternate, block and branch copolymerisation;
3. In addition to changing the types of repeating units, the relative amounts of
each monomer used in the reaction may also be varied to produce literally an
unlimited number of possible combinations of properties.
4. This concept gives the possibility of “tailor-making” or “engineering” the
plastic material desired.
5. There are a great number of copolymer which are synthesised to meet
different application requirements. The copolymer synthesised using three
monomers of acrylonitrile, butadiene and styrene and are ABS which is a
widely used plastics, Z
 Different Types of Copolymers

Alternate Block

Graft or Branch Random

=Monomer A =Monomer B
Z
 ABS: A Typical Copolymer

A B S
Z
 ABS: A Typical Copolymer

A B S
Z
SBR: Styrene-Butadiene Rubber Acrylonitrile
Poly
NBR: Acrylonitrile-Butadiene Rubber
SAN: Styrene-Acrylonitrile Copolymer
A
HIPS: High Impact Polystyrene

ABS
SBR HIPS
B S
Poly Butadine S
Poly tyrene

ABS Resin Phase Diagram

 Typical ABS Grades
1. General Purpose
2. High Strength
3. Transparent
4. Electroplatable
5. UV Resistant
6. Flame Retardant
7. Glass Filled
8. Antistatic
9. Flame Retardant
10. High Mouldability
11. Heat Resistance
12. High Impact Resistance
13. Laser Markable
Z
 Polymerisation

Addition Polymerisation Condensation Polymerisation

One monomer with More than one monomer Two monomers with two
double bond with double bond functional groups at both ends

Homo-polymers Co-polymers Condensation polymers

Polymer Blends and Alloys Filled Polymers

(Homo-polymers + Co-polymers + (Polymer + Additives)
Condensation polymers)

Methods of Producing Different Polymer Materials

 NaOH + HCl NaCl + H2O
sodium hydroxide + hydrochloric acid sodium chloride + water

Neutralisation
A neutralization reaction is when an acid and a base react to form water and a salt
and involves the combination of H+ ions and OH- ions to generate water.
The neutralization of a strong acid and strong base has a pH equal to 7.

H3C-COOH + HO-CH2-CH3 → H3C-CO-O-CH2-CH3 + H2O

ethanoic acid + ethanol ester + water

Esterification
When a carboxylic acid is treated with an alcohol and an acid catalyst, an ester
is formed (along with water). This reaction is called the Fischer esterification. Z
 Condensation Polymerization
1. Polymer chains can be also formed by step-growth condensation reactions
polymerisation, producing structures and properties that resemble those of addition
polymers.
2. A relatively small molecule (such as water, ethanol, methanol etc.) is produced as a
result of polymerisation reaction.
3. It often involve different monomers as starting or precursor molecules.
4. Polyester is synthesised by condensation polymerisation. A hydrogen atom on the end
of the ethylene glycol monomer combines with and OH. Water is condensed off and
two monomers combine to produce a larger molecule.
5. Each of the monomers is bi-functional and condensation polymerisation can continue
by the same reaction. Eventually, a long polymer chain (polyester) is produced.
6. The repeat unit for this polyester consists of two original monomers; one ethylene
glycol and one dimethyl terephthalate.
7. Polymer chain length depends on the ease with which the monomers can diffuse to the
ends and undergo the condensation reaction.
8. Chain growth ceases when no monomers reach the chain ends to continue the reaction.
Z
Condensation Polymerisation of Polyester Z
Condensation Polymerisation of Polyamide 66 Z
Polymer Structures

Z
 Performance

Processing

Composition Microstructure

Materials Tetrahedron Z
 Diamond Versus Graphite
1. In diamond, each atom is bonded tetrahedral to four others, making 3-
dimensional network.
2. In graphite, each carbon atom is covalently bonded to three other
surrounding carbon atoms. These exist in layers, which are not covalently
connected to the surrounding layers. Instead, different layers are connected
together by weak forces.
3. The flat sheets of carbon atoms are bonded into hexagonal structures.
4. Diamond is the hardest mineral known to man but graphite is one of the
softest materials.
5. Both diamond and graphite are good thermal conductors.
6. Diamond is the ultimate abrasive, but graphite is soft and a very good
lubricant.
7. Diamond is an excellent electrical insulator but graphite is a conductor of
electricity because it can conduct electricity due to the vast electron
delocalization within the carbon layers. These electrons are free to move, so
are able to conduct electricity.
8. Diamond is usually transparent, but graphite is black and opaque.
9. Diamond is very expensive and used as jewellery but graphite is cheap and
used as electrodes, pencil and lubricants. Z
Diamond Versus Graphite

Z
 Materials Equipment

Findings: The ultra-thin material Andre Geim and Konstantin Novoselov:

called graphene Nobel Prize Winner in Physics 2010
Illustration of Amorphous, Semi-crystalline and
Orientation of Polymer Chains
Z
 At Manufacturing
Temperature

Transparent Transparent

At Ambient
Temperature

Translucent Transparent

Semi-crystalline Amorphous
Thermoplastics Thermoplastics

Semi-crystalline VS Amorphous Thermoplastics Z

 Typical Semi-crystalline and Amorphous Plastics

Typical Semi-crystalline Typical Amorphous

Thermoplastics Thermoplastics
Low density polyethylene (LDPE) Polystyrene (PS)

High density polyethylene (HDPE) High Impact Polystyrene (HIPS)

Polypropylene (PP) Acrylonitrile butadiene styrene copolymer (ABS)

Polyamide (PA) Polyvinylchloride (PVC)

Polyethylene terephthalate (PET) Polycarbonate (PC)

Polyebutylene terephthalate (PBT) Polymethyl methacrylate (PMMA)

Polytetrafluoroethylene (PTFE)

Polyoxymethylene (POM)

Z
Effect of Crystalline and Amorphous Structures on
Properties and Performance of Polymers

Property Crystalline Amorphous

Density Higher Lower
Strength Higher Lower
Modulus Higher Lower
Ductility Lower Higher
Resistance to creep Higher Lower
Max usage temperature Higher Lower
Shrinkage Higher Lower
Warpage Higher Lower
Hardness Higher Lower
Wear resistance Higher Lower
Transparent Lower Higher
Chemical resistance Higher Lower Z
Computation of the Percent of Crystallinity
of Semi-Crystalline Polymer
The percent of crystallinity 𝑋𝑐 by weight can be determined from
accurate density measurements by using equation below.

𝜌𝑐 (𝜌𝑠 − 𝜌𝑎 )
𝑋𝑐 = × 100%
𝜌𝑠 (𝜌𝑐 − 𝜌𝑎 )

𝜌𝑎 is the density of the totally amorphous polymer;

𝜌𝑐 is the density of the perfectly crystalline polymer;
𝜌𝑠 is the density of the semi-crystalline polymer sample;
 Computation of the Percent of Crystallinity of
Semi-Crystalline Polymer
A HDPE sample has 𝜌𝑎 = 0.870 𝑔/c𝑚3 , 𝜌𝑐 = 0.998 𝑔/c𝑚3 and 𝜌𝑠 =
0.925𝑔/c𝑚3 . Compute the percent of the crystallinity of this HDPE.

𝜌𝑐 (𝜌𝑠 − 𝜌𝑎 )
𝑋𝑐 = × 100%
𝜌𝑠 (𝜌𝑐 − 𝜌𝑎 )

0.998 × (0.925 − 0.870)

= × 100%
0.925 × (0.998 − 0.870)

= 46.36%
 Computation of the Percent of Crystallinity of
Semi-Crystalline Polymer
If the percent of crystallinity of the HDPE is increased to 58.00% by
slow cooling, determine the density𝜌𝑠 .
𝜌𝑐 𝜌𝑎
𝜌𝑠 =
𝜌𝑐 − 𝑋𝑐 (𝜌𝑐 − 𝜌𝑎 )

0.998 × 0.870
=
0.998 − 0.58 × 0.998 − 0.870

0.86826
=
0.998 − 0.07424

0.86826
=
0.92376

= 0.940 (𝑔/c𝑚3 )
 Characteristic Temperatures of Polymers

Glass Transition Temperature (Tg): The temperature at which the amorphous polymer
change from rubbery state to solid state or vice versa. Polymers have different specific heat
capacity before and after glass transitions. Elastomers should have a lower Tg than
ambient temperature to retain the elasticity;

Melting Temperature (Tm): The temperature at which the solid crystalline will melt when
being heated up. The melting temperature is a range due to the different sizes of crystal
structures. It is an endothermic event.

Crystallization Temperature (Tc): The temperature at which the liquid polymer chain will
crystallize when being cooled down. The crystallization temperature is a range due to the
different sizes of crystal structures. It is an exothermic event.

Curing Temperature Tcuring: The temperature at which the thermoset resin and hardener
start reacting and becomes permanent solid. It is exothermic event.

Decomposition Temperature (Td): The hydrocarbon molecular chains are thermally

broken. Oxygen will exacerbate the decomposition and it is referred to as oxidization. It is
an exothermic event.
Z
Snake Segment Movement
 Glass Transition and Melting
Temperatures of Different Polymers
Polymer Symbol Tg (0C) Tm (0C)
Low Density Polyethylene LDPE -100 120
High Density Polyethylene HDPE -70 135

Polypropylene PP -30 165

Polyvinyl Chloride PVC 85
Polystyrene PS 90-100
Polyethylene Terephthalate PET 70 256
Polycarbonate PC 155
Polyoxymethylene POM -13 165
Polyamide 66 PA 66 50 260
Polyamide 11 PA 11 45 165
Polymethyl methacrylate PMMA 105
Z
Stress

Strain

Strain Hardening of Polymer Z

 Heat Shrink Tubing Heat Shrink Wrapping

Applications of Polymer Chains Orientation

Commonly Used Thermoplastics
• Low Density Polyethylene (LDPE)
• High Density Polyethylene (HDPE)
• Polyvinyl Chloride (PVC)
• Polypropylene (PP)
• Polystyrene (PS)
• High Impact Polystyrene (HIPS)
• Acrylonitrile-Butadiene-Styrene Copolymer (ABS)
• Polyethylene Terephthalate (PET)
• Polybutylene terephthalate (PBT)
• Polyamide (PA)
• Polycarbonate (PC)
• Polyoxymethylene (POM)
• Polymethyl Methacrylate (PMMA)
• Polyethersulfone (PES)
• PEEK(Polyether Ether Ketone)
Z
 Polymerisation

Addition Polymerisation Condensation Polymerisation

One monomer with More than one monomer Two monomers with two
double bond with double bond functional groups at both ends

Homo-polymers Co-polymers Condensation polymers

Polymer Blends and Alloys Filled Polymers

(Homo-polymers + Co-polymers + (Polymer + Additives)
Condensation polymers)

Methods of Producing Different Polymer Materials

 Polymer Blends and Alloys
1. Blends are combinations of polymers that are mechanically mixed.

2. They do not depend on chemical bonding, but often require “compatibilizers” to

keep the constituents from segregating.
3. When the combination of polymers produces a product that has a single glass
transition temperature and that exhibit a synergistic effect in properties, the
product is called an alloy.
4. When the combination produces a product with multiple glass transition
temperatures and with properties that are average of the contributions of the
individual constituent polymers, the product is called a blend.
5. To keep the constituents of a polymer blend from separating , especially when
they are chemically incompatible, compatibilizers are added to the mixture. The
compatibilizer is a material that has an affinity to both polymers to be mixed.
6. Polymers with improved mechanical performance and added features can be
created by polymer blending and alloying.
Z
 Blend and Alloy Systems
Materials Properties
PPO/PS Polyphenylene oxide (PPO) has a high strength and high heat
resistance but oxidizes at temperatures required for processing:
adding polystyrene (PS) makes it possible to process.
ABS/PC Acrylonitrile-butadiene-styrene (ABS) has lower cost and higher
processability while polycarbonates (PC) has higher toughness
and heat resistance.
PC/PET PC, though tough and able to withstand very high temperatures,
PC/PBT lacks good resistance to chemicals; polyethylene terephithalate
(PBT) makes up for this lack.
PET/PBT Alloying with PET lowers PBT’s impact resistance but bring
down its cost.
PVC/ABS Polyvinyl chloride (PVC) adds flame retardance and rigidly to
ABS, a more easily processed resin.
PP/Elastomer Polypropylene (PP) contributes a good heat resistance and
processability; elastomers add impact resistance. Z
Additives for Filled Polymer
• Fillers (extender, dimension)

• Reinforcements

• UV Stabilizers (Prank, rubber)

• Heat Stabilizer (PVC)

• Plasticizers (Synthetic Leather)

• Fire Retardants (Cooling, Foaming, Dilution))

• Smoke Suppressants

• Magnetic Powders

Z
 Additives in Polymer

• Colorants & Pigments (Phone cables, aesthetics)

• Antistatic Agents (Petrol Tank, Mine Pipe)

• Lubricants
• Nucleating Agents (Size VS Crystalline)
• Antioxidants (PE, Food Packing )
• Processing Aids
• Fungicides (Cable and ester)
• Foaming Agents (Packing)
Z
Steel and Plastic Fuel Tanks for Cars
 Word Equation of Five Techniques to Produce Different Polymer
Materials with Wide Range of Properties and Attributes

Same Monomers With Double Bonds Addition Polymerisation Polymer

Examples: HDPE, PP, PVC, PMMA, PS

Monomers of A With Double Bond +Monomers of B With Double Bond Addition Polymerisation Copolymer

Examples: HIPS, ABS, SBS

Condensation Polymerisation
Monomers A With Bi-functional Group +Monomers B With Bi-functional Group Polymer

Examples: PC, PA, PET

Polymer A + Polymer B Simple Mixing Polymer Blend or Alloy

Examples: PC/ABS, PA/PE, ABS/PVC

Compounding
Polymer A + Additives Filled or Functional Polymers
Examples: CaCO3 filled HDPE, glass fibre reinforced PA, carbon black filled PVC
Z
 Additives
Polymer
Filled
Polymer

Additives
Polymer A+ Polymer B=
Polymer Blend
 Materials Classification
Metals Polymers Ceramics Composites

Polymers

Synthetic Polymers Natural Polymers

Wood Fibre Resin

Plastics Elastomers Adhesives

Synthetic
Fibres
Thermoplastics Thermosets
Z
 Classification of Elastomers (Rubbers)

Elastomers
(Rubbers)

Vulcanised Thermoplastic
(thermoset) Elastomers
Rubbers

Z
 Stretching of
Bonds

Uncoiling of
Chains

Stress-Strain Curve for an Elastomer Z

Features of Elastomers

1. Sealing
2. Flexibility
3. Slip resistance
4. Shock absorption
5. Vibration resistance
6. Comfort
7. Texture

Z
 Uses of Condom Other Than for Sex

1- Balloon animals for the kids

2- Smuggling drugs
3- Water balloon fights
4- Temporary leg bottom cover to avid floor scrapes
5- Waterproof change purse
6- Bathing cap
7- Doggie rain booties
8- Homemade catnip toy
9- Slingshot band replacement
10- Tie around arm when donating blood
11- Ice pack
12- Temporary help to stop water pipe leaks
13- Golf club covers in the rain
14- Hacky-sack
15- Disposable baggie for small dead animals/bugs
16- Makeshift weapon if filled with rocks or coins
17- Live bait holder for fishing
18- Finger protector when unclogging a sink drain
19- Crime scene evidence baggies
20- Rifle barrel protector
21- Twist ties
22- Bird seed holder
Microsoft Macrohard 23- Soil sample container
24- Paint holder
Condom 25- Drain stopper