(Bio- and Nano-)

Materials Engineering
Day 02
 Course (Module) Plan

Week Topic Question Set

1 – Tue 9 Feb Hydrophobicity 1
2 – Tue 16 Feb Surface Tension + Thin Films 2
3 – Tue 23 Feb Biomaterials (part 1)
3
4 – Tue 2 Mar Biomaterials (part 2)
5 – Tue 9 Mar Electron Microscopy
4
6 – Tue 16 Mar TEM Visit* (+ intro to Phase Diagrams)
5
7 – Tue 23 Mar Phase Diagrams

 *TEM visit:
 Date TBC, pending equipment setup at Centre for Advanced Microscopy
 Will require some outside of 5-7 pm attendance, further details to come
Day 4 Lab Activity
(part a)
 Materials and Equipment

PPE Materials/Equipment
 n/a  Large container
 Stirring spoon
 6 cups water
 0.5 cup dish washing soap
(preferably Fairy)
 1 tablespoon glycerine
 0.5 cup corn starch
 2 tablespoons baking
powder
 Giant Bubble Fluid

Ingredients Instructions
o 6 cups water Avoid creating too many bubbles

o 1/2 cup dish washing soap 1. Dissolve corn starch in water

(preferably Fairy) (requires a lot of stirring)
2. Add remaining ingredients, stir
o 1 tablespoon glycerine
3. Allow to sit for 1 hr (or more),
o 0.5 cup cornstarch stirring occasionally as corn
o 2 tablespoons baking powder starch settles

Note: corn starch will likely not fully

dissolve, bubbles will still work
Giant Bubble Fluid - Trials

Trial Special Instructions

A Original recipe, no changes
B Commercial product (follow instructions on bottle)
C Substitute personal lubricant instead of glycerine
D Remove baking powder
Content Hidden
E Remove corn starch
F Substitute 2x personal lubricant instead of
glycerine and remove backing powder and corn
starch
Surface (or Interfacial)
Tension
 Surface (Interfacial) Tension

 The surface is tense because

it’s not surrounded by
familiar/similar material
 Human surface tension can
be observed in lecture halls →
no one wants to sit at the front
Related to Hydrophobicity

 In both, material behaviour is influenced by the desire not to interact with different
materials
 Surface tension generally refers to the tension at an interface between air and some
liquid, interfacial tension refers to the tension at any interface between multiple materials
(eg: oil and water)
 Tension means energy, occupying a high tension state requires more energy, and laziness
is a fundamental truth of the universe → everything wants to be in the lowest energy state
possible
Surface Tension
When you see the word ‘surface’ think nanotechnology
Gravity vs Surface:
“Molecular Politics”
Gravity Says:
 “I don’t want anything to be up! Bugs
belong at the bottom!”
 Gravity wants the bring the full mass of
the bug down, but bugs don’t have
much mass
With more mass, gravity complains
more and the thing sinks
Surface Says:
 “I don’t want to touch anything! Bug legs
are icky!”
 Water doesn’t like bug legs, and wants to
limit the surface area of interface
between water and bug legs. And little
bug legs have a high surface area to
volume ratio.
With a less tense surface, the surface
complains less, and the thing sinks (eg:
bugs landing on soapy water sink)
Surfactants and Emulsifiers

 Like mix and match animals on a

molecular scale
 Or molecular mediators in (interfacially)
tense situations
 Molecules with hydrophobic and
hydrophilic portions, so each individual
molecule wants to interact with both
polar/aqueous and non-polar/organic
materials, forcing the two to mix
Why do we care? Examples

 The heat in high temperature washing is to improve wetting (ability of the liquid to fully
interface with the material) and essentially combat water’s high surface energy
(resistance to mixing with different things) – surface tension can be modified by improved
detergents instead, leading to energy savings and gentler washing
 Tents stay dry inside because the fine fibres don’t intrude much on water droplets, leaving
the water to mostly interact with air (which is does not like) and thereby allowing surface
tension to keep the water as exterior surface drops
 Paint finishes (which serve more than aesthetic purposes)
 Oil recovery depends on interfacial tension
 Stability in food products – emulsifiers are used in products like milk and ice cream that
contain immiscible components, overcoming the interface tension is required to keep the
materials in the desired form
 Surface Tension
in Capillary Action

 Surface tension provides

cohesion in fluids –
material sticks together
to avoid forming surfaces
– attraction between
molecules of the same
material
 Adhesion in the
attraction between one
material and another
 Adhesion causes
capillary action and
surface tension/cohesion
makes it to continuous

http://hyperphysics.phy-astr.gsu.edu/hbase/surten2.html#c4
 Surface Tension Application:
Cat Tongues

 https://www.youtube.com
/watch?v=zfBJmytIegs
 Start ~8:20
 Biomimetics is an
interesting branch of
nanotechnology
Electrospinning
Dissolving Polymers

 Polymers tend to be organic, non-polar

 Like dissolves like
 Common organic solvents:
 Acetone
 Chloroform
 Dichloromethane
 Ethanol
 Organic solvents tend to be very
volatile (evaporate easily)
 Organic solvents also have lower
surface energy than water
1. Dissolution of Material

Surface tension minimises

surface area: spherical
Meh. I suppose you lot are okay. shape end needle, as
much liquid as possible
stays in needle

    
    
 
 
Solution in Needle
 2. Application of Voltage

+ + +
+    +
 
+
Hi positive charge! It +

makes me so happy to 
bring you all the
- -
negative charge I can,
transported form all Charged Solution ☺ ☺
over the solution +
(cont’d)

Ew! You have a positive charge? I have a positive

charge! We can’t both be wearing the same charge!
I need to get away from you!

+ + +
+    +
 
+ +
 
- -
Charged Solution
☺ ☺
+
+
3. Taylor Cone Formation

-
Surface tension fights
Well hello there against this deformation
opposite charge, I because it creates
must say that I find
you very attractive + more surface area
☺
+ + +
+    +
 
+ +
 
- -
Charged Solution
☺ ☺
+
 5. Overcoming Surface
Tension

-
Ah! Neutralised!
So much better. ☺
Me next!
Without surface tension
+
holding most of the
solution together, the
☺
+ + +
+   
nanoscale Taylor cone
+

would not be forced

+
into existence +
 
- -
Charged Solution
☺ ☺
+
How Nanofibres Form

In the journey through the air the volatile solvents

evaporate, leaving only the solid polymer material

The jet emitted from the Taylor cone

is very thin, on the nanoscale
 Direct to Skin Electrospinning

 Electrospun nanofibres
have biomedical
applications
 Excellent for bandaging
applications
 Direct to skin → optimal
interfacing with
existing/healthy tissue
A battery-operated portable handheld electrospinning apparatus
June 2015 Nanoscale 7(29)
Surface Tension in
Bubbles
 Surface Tension in Bubbles

 Surface tension is responsible for the spherical shape of bubbles

 Spheres have minimal surface area
 Bubbles exist with surface tension trying to decrease the size (to reduce surface area) and
internal air pressure resisting the shrinkage
 Soap (surfactant) decreases surface tension of water
 and deceases bugs that land on that water

 Soap inhibits evaporation of water, the real deadly threat to bubbles, especially as
gravity pulls solution to the bottom of the bubble while the top thins
 But greater soap concentration leads to thinner bubbles as the surface tension is reduced

 Glycerol/glycerine is more powerful at preventing evaporation, used in consumer goods

to prevent drying out
 Long chain polymers, such as those found in guar gum and polyethylene oxide (PEO)
(used in industrial lubricants, e.g. J Lube) may be even better

Note: soap, glycerol, and long chain polymers also increase the elasticity of the material. Briefly, a
hole can’t form separating two regions of the bubble when there’s actually a big long molecule
connected to both regions. The science of giant bubbles includes but goes beyond surface tension.
Day 4 Lab Activity
(part 1)
 Materials and Equipment

PPE Materials/Equipment
 n/a  2x Dowel
 2x Eyelet screw
 3+ m Cotton rope
 1x Metal washer
 Bubble Sticks

1. Screw an eyelet screw into the end of

each of 2 dowels
2. Optional: spray paint the wands
3. Cut 2 pieces of cotton rope, ~1 and 2 m
4. Feed large metal washer onto longer rope
segment (should move freely and have
enough weight to pull down the long rope
segment)
5. Feed one end of each rope through an
eyelet screw and knot in place, repeat
with the other ends through the other
eyelet screw
Colour
How to Be Colourful

 Perceived colour requires a particular wavelength of light reaching your eyes, and this
can be achieved many ways:
 Pigments: When presented with white light, molecules absorb some wavelength and reflect
others, which make it to your eye to see.
 Luminescence/emission: Light of a particular wavelength is produced (from incoming light,
chemical reaction, electronic excitation) from the material and makes it to your eye to see.
 Scattering: Light bounces around small particles (e.g.: in the atmosphere) differently depending
on wavelength, resulting in different wavelengths from a white light source making it to your eyes
from different locations (e.g.: the blue sky vs the bright yellow sun).
 Structural colour: Incoming white light reflects from a material from very slightly different
locations, making the reflected wavelengths slightly out of sync with each other such that
destructive interference occurs. Depending on the specific geometry of the material and
incoming white light, some wavelengths are just the right size to match phase, and only these
wavelengths make it to your eyes.
 And more: surface plasmon resonance, blackbody radiation… but we’re not going into these
Structural Colour – so pretty!
 Structural Colour vs Pigment

 Both do not produce light,

but appear a certain
colour under white light
 Pigment colour is at the
molecular level—if you
ground it up you’d get a
coloured powder
 Structural colour depends
on shape—if you grind up
the material it’s usually
brown

RSC Adv., 2013,3, 14862-14889

Thin Films
(and Bubbles)
 The multicolour appearance of bubbles,
soap films, and oil slicks is a structural
colouration due to the nature of thin films
 Light reflecting from the outside and inside
edges of the film interfere
 Only wavelengths experiencing constructive
interference are seen
 As this depends on angle, the colour
appears to change
Interference

 Waves exactly in phase will interfere constructively

 Waves exactly out of phase will interfere
destructively (cancel out)
 A mish mash of slightly out of phase waves will
average out to destructive interference
Thin Film: Step by Step

 The process:
 Light hits the outside interface between air and film
 Some is reflected (incident angle determines path)
 Some is transmitted (refractive indices and incident angle
determine path)

 Transmitted (and refracted) light hits the inside barrier, the

same two options occur, reflect and transmit
 Reflected light travels back to the first interface, and again
reflection and transmission occur
 Transmitted (and re-refracted) light exits to re-join the originally
reflected light – but it took a longer path to get there

 The difference in phase is determined by the different in

optical path length
 Note: ½ phase change occurs when reflecting from a
higher refractive index material
 Assume all wavelengths experience both reflection and
transmission
Thin Film: The Math

“D” is the point along the first reflection path at

which the second path re-joins, with both paths
again coherent, parallel, in sync

 More details at: http://hyperphysics.phy-astr.gsu.edu/hbase/phyopt/soapfilm.html#c1

Thin Film: The Math

 Γ = optical path length difference

 n = refractive index of the
film(assuming light initially travels
through air)
 d = film thickness
 β = angle within film between light and
normal/perpendicular line (determined
from refractive index n and incident
angle α)
 α = initial angle in air between light
and normal/perpendicular line
 m = integer value (1, 2, 3, …) to ensure
whole number of wavelengths (or
whole number minus half in case of
phase change on reflection)
 λ = wavelength of light

 More details at: http://hyperphysics.phy-astr.gsu.edu/hbase/phyopt/soapfilm.html#c1

 Thin Film: Colours

Note the different angles

required for different
Incoming white light colours, to allow the
from multiple required path length
difference within the film
directions for different wavelengths.

At each angle, only

Light reflects from inner and one wavelength
outer boundary Thin Film experiences
constructive
interference and
reaches the eye
 Thin Film: Colours
At each angle, only one
Incoming white light wavelength experiences
from multiple constructive interference
directions and reaches the eye

Light reflects from inner and

outer bubble boundary Thin Film
For stationary eyes, the different colours require
different incident angles, and therefore appear
to come from different locations.
 Thin Film: Colours

Empirical verification at home

using ‘holo’ fabric backpack

Thin Film

Sunny Window Camera

 Thin Film: Colours

Theoretical verification using formula (see above)

2nd*cos(β) = 0.5λ
cos(β) = 0.5λ/2nd
β = cos-1(0.5λ/2nd)
(α proportional to β)
From 0 to 90°, cos() decreases with angle
Increasing λ → increasing cos(β) → decreasing β → decreasing α
 Bubble Colours

Note the different angles

required for different
Incoming white light colours, to allow the
from multiple required path length
difference within the film
directions for different wavelengths.

At each angle, only

Light reflects from inner and one wavelength
outer bubble boundary experiences
Bubble constructive
(spherical thin film) interference and
reaches the eye
 Bubble Colours

Incoming white light At each angle, only one

from multiple wavelength experiences
directions constructive interference
and reaches the eye

Light reflects from inner and

outer bubble boundary
Bubbles also have variations in film
thickness that produce colour variations
For stationary eyes, the
different colours require
different incident angles,
Bubble and therefore appear to
(spherical thin film) come from different
locations.
 Bubble Colours

Note the angles, for every line of

perceived light:
- the incident and reflected light
must exist at mirror angles
relative to the ‘normal’
(perpendicular) of the film where
the light hits it.
- The inner boundary light is
refracted and therefore changes
angle, but it is also refracted
back as it exits, so is parallel to
the reflected incident light when
it reaches the eye.

Bubble
(spherical thin film)
 Nanoscale Features

 Nanomaterials interact with light

differently to bulk materials
because the
materials/features/topography
are on the same scale as the
wavelength of light
 Scattering and diffraction occur
(the nanofeatures effectively
act as individual source points,
leading to more complex
interference patterns)
 We’re not going into this (just for
context)

https://physicsworld.com/a/a-flowers-nano-powers/
Why do we care?

COLOUR is easy to see!

nanoscale features are not
Why do we care?

 Many analytical techniques used for very small features* or amounts** ultimately rely on a
colour detection because that is much easier to visualise and quantify

* Small features are important in electronics manufacturing. Transistors (the heart of your
computers) are just shapes of differently treated and etched areas on a piece of silicon.
Making smaller and more powerful phones/computers depends on processing equipment
that can reliably manipulate nanoscale dimensions in silicon chips.

** Small amounts of biomolecules are important in medicine, both in diagnostics (e.g.:

detecting the one in a million cell to catch cancer early enough to treat) and in treatment—
controlling dose is important and many biomolecules require very small quantities. Detecting
small amounts is also important in analytical chemistry, forensics, or any area where greater
understanding of a material is required.

Fun Fact: flame emission analysis (looking at the colours produced from a material at
high energy—in a flame) can determine the atomic composition of a material and find
trace elements. A similar process is used to examine the composition of the sun and
other cosmic bodies. The theory is useful for very small things and very big things.
Anti Reflective Coatings
Thin Films in Photolithography

 Photo (= light) + litho (= stone) + graphy (= writing)

 Used to cut microelectronic patterns into silicon chips
 Cutting Si is easy, cutting very precise and small shapes is hard
 Thin Films in Photolithography

‘Masks’ partially block light shone on the silicon, so it

only reaches the silicon only in a specific pattern

Optics can be used to shrink the image on a ‘mask’

Thin Films in Photolithography

 Photoresist is a chemical that reacts under light, usually a free-

flowing chemical goop that solidifies when light is shone on it
 Silicon is sensitive to acid, but photoresist is not
 Fun fact: Often organic/polymer materials are immune to things
that react with inorganic/metallic/stone materials, and vice versa.
 Thin Films in Photolithography

 In photolithography (negative resist):

 A layer of photoresist is spread over
silicon
 Light shone through a mask causes
specific shapes in the photoresist layer to
harden
 The silicon is washed, removing
unhardened photoresist
 The silicon is etched in acid, but only the
exposed silicon is cut away by the acid.
The hardened photoresist protects a
specific shape of silicon.
 A different solvent is used to remove the
hardened photoresist. This is an organic
solvent that has no effect on silicon.
 End result: A very specific shape cut into
the silicon
Thin Films in Photolithography

 Why are thin films important?

 Light exposure must be carefully controlled so that the hardening
reaction occurs fully and only in the exposed area:
 Too little light: the reaction does not occur through the entire thickness
 Too much light: the reaction can spread sideways, which would alter
the pattern to no longer match the mask

 Consistency of film thickness is important for the same reasons

Example

 There is a thin film of oil (n = 1.46) on water (n = 1.33). You need

to know how thick the film is in order to work out how much oil
has spilled. At an angle of 30° from the surface of the water,
you see green light (λ = 550 nm). How thick is the film?
 Example
Solution by Steps

There is a thin film of oil (n = 1.46) on water (n = 1.33). You need to know how thick the
film is in order to work out how much oil has spilled. At an angle of 30° from the surface
of the water, you see green light (λ = 550 nm). How thick is the film?

Path difference must be 0.5 wavelengths from a whole

Half phase shift (1 < 1.46) number (m = 1, 2, 3…) of wavelengths
[path 2] – [path 1] = (m – 0.5)(550 nm)
[n(AB) + n(BC)] – [AD] = (1 – 0.5)(550 nm)

n=1 Refractive index (n) affects optical path length in AB and

30°
30° BC (within the oil), but not in AD (in air) where n = 1

n1λ1 = n2λ2
n = 1.46 d=? λ2 = λ1(1)/n2  wavelength reduced in oil

• So more wavelengths fit/travel/wiggle through the

same physical space
n = 1.33 • So optical path in terms of wavelength needs to
account for extra wavelength travel by a factor of n
(refractive index in film).
No phase shift (1.46 > 1.33)
 Example
Solution by Steps

There is a thin film of oil (n = 1.46) on water (n = 1.33). You need to know how thick the
film is in order to work out how much oil has spilled. At an angle of 30° from the surface
of the water, you see green light (λ = 550 nm). How thick is the film?

Path difference must be 0.5 wavelengths from a whole

Half phase shift (1 < 1.46) number (m = 1, 2, 3…) of wavelengths
[path 2] – [path 1] = (m – 0.5)(550 nm)
[n(AB) + n(BC)] – [AD] = (1 – 0.5)(550 nm)

n=1
30°
30°
n = 1.46 d=? Start by assuming m=1. This is easiest/simplest, but remember
it can be any integer number.

n = 1.33

No phase shift (1.46 > 1.33)

 Example
Solution by Steps

30° 60°
A C
x=?

Snell’s Law (refraction):

1 * sin(60°) = 1.46 * sin(90° - x) d
sin(90° - x) = sin(60°) / 1.46
90° - x = sin-1(sin(60°) / 1.46)
x = 90° - sin-1(root(3)/ (2*1.46))
x = 90° - sin-1(root(3)/ 2.92)
x = 90° - 36.38°
x = 53.62 ° B
 Example
Solution by Steps

SOHCAHTOA (right angle triangles): D

sin(53.62°) = d/AB ?
AB = d*(1/ sin(53.62°) )
(note: BC = AB) 30° ? 60°
A C
53.62°
tan(53.62°) = d / (AC/2)
AC = 2d*(1/tan(53.62°) )
d
?
cos(30°) = AD/AC
AD = cos(30°)*AC
AD = cos(30°)*2d*(1/tan(53.62°) )

n(AB) + n(BC) – AD = (1 – 0.5)(550 nm)

B
 Example
Solution by Steps

n(AB) + n(BC) – AD = (1 – 0.5)(550 nm)

2*1.46*(d*(1/ sin(53.62°) )) - cos(30°)*2d*(1/tan(53.62°) ) = (1 – 0.5)(550 nm)
d*( (2*1.46/sin(53.62°)) – (2*cos(30°)/tan(53.62°)) ) = 275 nm
d = 275 nm / ( (2*1.46/sin(53.62°)) – (2*cos(30°)/tan(53.62°)) )
d = 116.98 nm

Not done yet! Sanity checks:

• Check the value → same result from slightly different formula in above
slides

• Check the sense → general order of magnitude, d < [overall path

length] as the path length will go down d and back up again on an
angle
 Example
Solution by Formula

There is a thin film of oil (n = 1.46) on water (n = 1.33). You need to know how thick the
film is in order to work out how much oil has spilled. At an angle of 30° from the surface
of the water, you see green light (λ = 550 nm). How thick is the film?

Half phase shift (1 < 1.46) Identify that there is a phase shift

Select appropriate formula from slides

n=1
30°
30°
n = 1.46 d=?
Rearrange formula to solve for d
d = (m – ½)*λ / 2*n*cos(β)

Solve
d = (1 – ½)*(550 nm) / 2*(1.46)*cos(β)
n = 1.33 Need Snell’s law for angle β ( = 90° – 53.62° = 36.38° )
(from previous slides)
No phase shift (1.46 > 1.33) d = 116.98 nm
Day 4 Lab Activity
(conclusion)
 Make Giant Bubbles!

 Carefully carry the

solutions and wands
outside
 Do not move wands
between recipes
 Dip the ropes fully into
the bubble fluid and
slowly lift out (separate
wand sticks for larger
bubbles), wave gently
to make bubbles
 Take notes to compare
recipes A-F
 Take pictures!
Closing Notes

 Question Set 2 posted to wattle

 Photos of pracs? Please tag @therainbowscientist on Instagram
 Next week: Biomaterials (part 1), no special requirements