2-ICI Binders - Final

Shell Binders
ICI Industry Certification Program

1
Unit Objective
• Understand the types of silica and non-silica
based binders
• Colloidal silica stability
• Understand the binding and gelling process of
colloidal silica
• Understand the relationship between mold
properties and silica particle size and
concentration
• Understand the usage of other binder additives
ICI Industry Certification Program 2

Liquid Components of a Slurry
• Binder
• Polymer/latex
• Water
• Wetting agent
• Antifoam
• Biocide

Binder
• A Good Binder must…

• Provide a high temperature bond
• Have low thermal expansion
• Have a manageable stability (ease of
use)
• Be economical

Binders
Three main types of binders
• Colloidal silica
– Water based
• Ethyl silicate
– Alcohol based
– Being phased out due to EPA
regulations
• Non – silica based binders

Colloidal Silica

6
Colloidal Silica
• What is colloidal silica?
• How does colloidal silica work?
• Why use colloidal silica?

Forms of Silica
Silicon Dioxide Si + O2 = SiO2
Crystalline Amorphous
Liquid Dry
Colloidal Fumed: 1000 nm

Silica Precipitated: 2000 nm
4 - 100 nm Gel: 1000-20000 nm

What is Colloidal Silica?
» Colloidal silica - Refers to a stable dispersion
of discrete amorphous particles of silicon
dioxide.
» amorphous - non-crystalline
» dispersion - a scattering
» Also referred to as a “silica sol”
Colloidal Silica products

are clear to milky-white,
depending on particle size.

Colloidal Systems
Dispersion Media
Solid Liquid Gas

Dispersed Phase
Solid Alloy Sol Aerosol
Liquid Gel Emulsion Fog
Gas Solid Foam

Foam

What does a colloidal silica particle
look like?

How big is a colloidal silica
particle?
What is a nanometer?
ICI Industry Certification Program12

S1 Stucco (450,000 nm)
Latex Polymer
(200-300 nm)
Colloidal Silica
(7 -13 nm)
Relative Sizes
Fact: A nanometer is one
billionth of a meter
Fact: A human hair is about
10,000 nm in diameter!

Let’s Think of It
Another Way…
=
A mass of silica the The amount of
size of a super-ball colloidal silica
has a surface area dispersed in water
of 50 cm2 in a coffee cup

In Colloidal Form, That One Ball of
Silica Has Now Become 16 Trillion
Little Spheres!
The total surface area is now

roughly 4,000,000 cm2 !

That’s enough surface area to
cover over 9 football fields!

16
Why don’t the particles sink?
Brownian Motion Brownian forces
overcome the force of
gravity
SiO2
SiO2 SiO2
SiO2 SiO2
SiO2 SiO2
SiO2
SiO2 SiO2

So what’s Brownian Motion?
•In 1827 the English botanist Robert Brown noticed
that pollen grains suspended in water jiggled about
under the lens of the microscope, following a zigzag
path.
•Even more remarkable was the fact that pollen grains
that had been stored for a century moved in the same
way.
•The first mathematical theory of Brownian motion
was developed by Einstein in 1905 at the same time as
his theory for special relativity
•For colloidal silica, the random movement of water
molecules due to temperature keep the particles
suspended

Brownian Motion
Demonstration
Brownian Motion\brownian.html

Colloidal Silica Stability
• van der Waals forces want to bring our
16 trillion spheres back into one single
sphere of silica
• We use ionic forces to keep the van der
Waals forces in check
• A lot of effort in the shell room goes
into controlling these relationships

Colloidal Silica, Stabilization,
and pH

Colloidal Silica
Stability versus
pH
Metastable
(steric)
Stable
(charge)
Increased
Stability
unstable
1 2 3 4 5 6 7 8 9 10 11
pH

What is pH and what does it
mean?
• pH = - log [H+]
• So what?
– pH is a way of describing the amount of H+ in
an aqueous (water) environment
• Well, what’s H+?
• H+ is a proton
– An acid is a material that gives H+ to a system
– A base is a material that receives H+

The “Yen and Yang” of pH
• OH- is “hydroxide”
• An acid gives up H+
• A base gives up OH-
OH-
• pH is a measurement of H+
• When pH = 7, the amount of H+
and OH- are the same H+
• Water is the “balance” point
• When I add water to my slurry,
why doesn’t it reduce my pH?
The pH Scale
• When pH < 7
– There is more H+ than OH-
– System is “acidic”
• When pH = 7
– There are equal amounts of
H+ and OH-
– System is “neutral”
• When pH > 7
– There is more OH- than H+
– System is “basic”

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The pH scale
• Adding water to
my slurry does Stomach acid
Antacid
not lower the pH =1
pH =10
pH, because
water has no
“activity”
meaning there 2 7 8 9
Activity
are equal
amounts of H+
and OH-
• Adding an acid
would
drastically
reduce my
slurry pH, and
gel the colloidal pH=0 pH=14
silica

Silica Surface
Na+ When the pH is basic,

Si-OH- + hydroxyl (OH-) groups
Na - give the particle a
Si-OH
charged surface
Si-OH-
Si-OH-
- A small amount of
Si-OH sodium (Na+) actually
Na+
helps stabilize the
Si-OH-
particle, by attracting
Na+ more (OH-)

Electrical Repulsion
Stability
Stability created by electrostatically
inhibiting collisions
SiO2
SiO2
Na+
SiO2 SiO2

How a drop in pH affects
colloidal silica
As pH drops…
Na+
OH- OH- Na+
OH- OH-
OH- OH- OH-
OH- OH-
Na+ SiO2 Na+
pH Na+ SiO2 Na+
OH- OH- OH- OH-

OH-
OH-
OH- Na+ OH- OH- Na+
• There are fewer OH- attached to the surface,

• Which results in a lower ionic force available to keep the particles apart
• Now instead of repelling each other when they collide, they stick to each
other and form a gel… in your slurry

Other Stability Factors

30
31
32
Stability - Effects of pH
and Particle Size
70 nm
20 nm
Increased Stability
4 nm
1 2 3 4 5 6 7 8 9 10 11

Concentration and
pH Effects
10%
concentration
Increased
Stability
30%
concentration
1 2 3 4 5 6 7 8 9 10 11
pH

35
36
Ionic Strength Effects
2000 - 7000 mhos

Increased Stability
<2000 mhos
>7000 mhos
1 2 3 4 5 6 7 8 9 10 11
pH

38
Negative Synergy in Slurries
% SiO2
32.0%
Tank #1
Moving Average is 30%
31.0%
30.0%
29.0%
28.0%
27.0%
26.0%
25.0% 11-Feb
15-Feb
10-Jan
16-Jan
21-Jan
25-Jan
13-Dec
19-Dec
10-Oct
15-Oct
19-Oct
24-Oct
29-Oct
3-Dec
7-Dec
12-Nov
16-Nov
21-Nov
28-Nov
1-Feb
6-Feb
2-Nov
7-Nov
Date

Negative Synergy in Prime
High % SiO2
+
+ Impurities
+ Low pH
+
= Short Slurry Life pH < 9.2
=
Energy
Input
Dispersed Aggregates

Stability Summary
• Colloidal silica is • Colloidal silica is less
more stable when… stable when…
• Larger particle sols are • Smaller particle sols
used are used
• When you maintain • When you let %SiO2
%SiO2 get too high
• When you control pH • When pH gets too low
• When you control the • When conductivity
ionic environment gets too high
• When you control • When a slurry gets too
slurry temperature hot

Colloidal Silica Reaction
• Colloidal silica particles are
polymerized spheres of silicon
dioxide
• The surface of these spheres
consist of un-reacted silica in
SiO2 Si OH-
+ - HO Si
SiO2
the form of silanol (SiOH-)
• When water is evaporating
from the slurry, the particles
are forced together
• Upon contact they bond in the
form of a gel
• This is a one way reaction –
once it has gelled, it cannot be
SiO2 Si O Si
SiO2 + H2O
recovered
• We want this to occur on the
shell, but not in the slurry!

So What Happens Next?
• Under green conditions (room
temperature), a gel network is formed
that hold the molds together
• Once the mold has been preheated,
sintering forms a permanent ceramic
bond that is much stronger

Colloidal Silica – Particle Size
• So if a larger particle colloidal silica is more
stable, then why not use it in all slurries?
• Because of…
• $
– The larger the particle, typically the higher the
cost of manufacture
• Strength
– The smaller the particle, typically the higher the
strength at a given %SiO2

Colloidal Silica Manufacture
Sodium 30% Silica
Silicate Product
Concentration
Ion Exchange
Silicic 5-6% Silica

Acid Product
Nucleation
&
Growth

Colloidal Silica - Particle Size
• Small particle binders
– 7-9 nm
– Low cost
– Less stable
– Popular for backups
– Fair draining and flow characteristics (rheology)
• Large particle particle binders
– 11-16 nm
– More stable
– Commonly used in primary slurries
– Good rheology

Colloidal Silica - Particle Size
• Very large particle binders
– 10 - 150 nm, 50% silica
– Lower water content, so faster drying, but
highest cost
– Good rheology
– Poor knockout

Colloidal Silica - Strength
22% 26% 30%

Small Particle
Large Particle
Strength
% Silica
• Ultimate strength dependent on particle size and concentration
• More silica is not always better!

Strength Example #1
Green Modulus of Rupture
Nalco 1130 + Latrix 6305
12
MOR (psi) 10
8
380.000
410.000 6
% Polymer
440.000
470.000
500.000 4
530.000
560.000
590.000 2
620.000
650.000
680.000 0
710.000
740.000
770.000 -2
above 21 22 23 24 25 26 27 28 29 30
% Silica
• Small particle binder, latex polymer

• P1/P2 flour blend
• Optimum strength around 8% polymer, 23-28% silica

Strength Example #2
Strength Comparison Between Binder Particle Sizes
800
700
Room Temperature Strength (psi)
600
500
400
300
200
100
Large Particle Small Particle

Backup Slurry Binder
• This foundry converted from a large particle binder to a small particle

binder in their backup slurry
• Not only was there a strength improvement, but there was a cost
advantage as well since they were using a less expensive colloidal
silica, at a lower % silica level

Colloidal Silica – Health and
Safety
• Colloidal silica is a fairly benign material
• HMIS rating of “1” on a 0 – 4 scale, with
“4” being the highest health risk
• No hazardous ingredients
• This being said, it will still irritate eyes and
skin (dries out skin really fast) so wear PPE
• It is messy – can be difficult to clean up or
remove once dried
• Ruins clothes too

Colloidal Silica - Summary
Positive aspects
• Environmentally friendly - water is the solvent,
no volatile organic compounds (VOC) concerns
• Abundance - investment casting is a minor
application of colloidal silica
• Ease of use – straightforward application if
controlled
• Easy to control - simple tests required
• Cost - relatively inexpensive

Colloidal Silica - Summary
Negative aspects
• Long final dry times - 24 to 48 hours to completely
remove moisture (see following presentations)
• Presence of sodium can cause problems in some
applications
– Sodium is a flux for ceramics, in that it can make the ceramics
turn soft at lower temperatures
– This can result in deformed molds and deformed castings
• Drying sensitive - colloidal silica shrinks as it dries. This
shrinkage can cause stresses that might lead to surface
defects in shell (see following presentations)
• pH sensitive

Ethyl Silicate Binder
• An alcohol based binder that is based on

Tetraethyl Orthosilicate (TEOS)
• Consists of large polysiloxane polymer
species
• Most common form is “prehydrolyzed”
or ready to use

Ethyl Silicate
Positive Aspects
• Fast “dry” times due to volatile solvent
• Can be gelled with ammonia
• Thin slurries
• Good green strength

Ethyl Silicate
Negative Aspects
• Government Regulations - Volatile
Organic Compounds (VOCs)
• Unpleasant working environment
• Short slurry life & more difficult to
control
• Flameproof equipment required
• Higher insurance premiums

Non – Silica Based Binders
• Used for special refractory applications
– increased refractoriness and less
reaction with metals during casting
• Ammonium zirconium carbonate
• Colloidal alumina

Polymers

58
Polymers
• Polymers are very large molecules containing
hundreds or thousands of atoms
• Examples of natural polymers
– Protein
– Nucleic acid (used to make DNA)
– Cellulose
• Most man-made (synthetic) polymers are organic,
meaning that they contain carbon
• Synthetic polymers are very large molecules made up
of repeating units of smaller molecules
• Examples of synthetic polymers are…
– Nylon
– Dacron
– Plexiglas
– Saranwrap

Latex Polymers
• Latex Polymers are…
• An Emulsion (what’s an emulsion?)
• A Latex can be defined as a dispersion of a
polymer in water
• The polymer dispersed in the water is in the
form of a micelle (see next slide)
• Primarily made of styrene and butadiene
– The ratio of each ingredient affects stiffness,
tackiness
• Typically 50% water
• Typically have an S.G. of nearly 1.00 g/ml

Latex Polymer Micelles
200 – 300 nm
In diameter

How Latex Polymers Work
• When added to a slurry, most of the
micelles stay emulsified because the
slurry is also aqueous 1.
• When the slurry coats the patterns,
millions of the spheres coat the part
(1)
• Upon drying, in the absence of water Part
the spheres can no longer remain
dispersed
• The polymers uncoil, react with each
2.
other, and form a continuous web
across the surface (2)
• This is a one-way reaction, meaning
that subsequent dips cannot re-
disperse previous polymer layers

Positive Aspects of Latex
Polymers
• Acts like a “glue” giving prime slurries better adhesion to the
wax
• Improved casting surface quality. Allows for shell flexion,
while maintaining dimensional stability, thus reducing surface
defects such as buckling, lifting, and cracking.
• Increase green strength (pre-fired) of shell
• Improves stucco adhesion – increases stucco pickup
• Changes the rheology, or flow characteristics of the slurry,
improving its coating efficiency.
• Allow for better drying (before latex, shells took much longer
to dry)
• Helps fill slots and holes for stucco adhesion
• May allow you to reduce shell material usage based on a
lighter, but stronger shell
• From an EH&S standpoint, latexes are like colloidal silica –
very benign

Negative Aspects of Latex
Polymers
• Cost – latexes can be expensive, but their
common application speaks to their ability to
pay for themselves
• Rheology – If you are not prepared for the
change, the addition of polymers can make
slurries drain “faster”
• There is currently a debate in the industry as
to whether latexes provide benefits in the
autoclave – they are suspected to become
soft at autoclave temperatures

Water Additions
• Water is added to slurries because…
• The colloidal silica is purchased at 30%
concentration, but this is not the optimum for
strength
• Water will evaporate from slurries with use, and this
has to be replenished or the slurries will gel
• Distilled and de-ionized (DI) water are common
• DI tends to be more economical, while distilled
tends to be more pure
• There is potential for a small amount of organics to
still be present in DI water
• Again, tap water cannot be used because of
dissolved cations

Surfactants (Wetting Agents)
• Used to reduce the surface tension of the slurry
– Helps the binders wet out the flours when building
a slurry
– Can assist in filling holes and slots, wetting in
• Can be anionic (-), cationic (+) or nonionic
• Always used in prime, occasionally in backups
• Recommended dosages depends on % actives –
consult with supplier
• Some wetting agents have limited application
life in slurries – regular smaller additions
required to maintain wetting characteristics
• Some wetting agents have a limited shelf life

Antifoams
• Antifoams are a liquid additive that are
designed to break down foam and
bubbles
• Typically used in all slurry formulations
• Dosage depends upon % actives –
consult with supplier
• Antifoams will reduce the wetting
properties of surfactants
• Shelf life is limited

Biocides

68
Biocides
• Biocides are used to eliminate the growth of
bacteria, yeast and fungus in the slurry
• Can use bleach (sodium hypochlorite) in low
concentrations
– Increases sodium level in slurry which could lead to
destabilization
– Increased sodium level could cause dimensional
problems
• Other non-sodium based biocides available –
“Grotan” is common
• EPA limits the biocides available in a given
application
Biocides
• Treat biocides, even bleach, with the utmost respect
• “Bio” means “life,” and “cide” means “to kill”
• Most biocides used in this industry are corrosive
– Can cause a chemical burn
– Can cause permanent eye damage
• Not only is Grotan corrosive, but it is also a
sensitizer
• Chemicals classified as sensitizers cause
compounding allergic reactions with subsequent
exposures
• Grotan has an HMIS rating of “3” meaning “high”
health risk

Do I have to use biocides?
• Fact – we are working with
– aqueous systems (slurries)
– that are warmer than room temperature,
– and contain organic materials that are food for bacteria
• Fact – Bacteria are everywhere, and slurry infections
can come from unexpected sources
• If you are using up a slurry faster than bacteria have
the opportunity to replicate, then biocides may not
be needed
• Along the same line, primes tend to need biocide
more often than backups

How do I use biocides safely?
• Make sure you and the operators know the
correct dosage (Grotan maximum safe
dosage is 1500ppm of liquid weight, or
0.15%)
• Make sure you use the proper PPE
• Read the MSDS, and know where it is
located
• Make sure that the biocide does not “shock”
the slurry during application – apply as part
of a water addition

Sources…
• Chemistry of Silica, by Iler
• U. of Virginia for Brownian Motion
applet

Thank You!
For not sleeping during

this presentation.

74
End of Unit

75

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Shell Binders

ICI Industry Certification Program

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• A Good Binder must…

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Colloidal Fumed: 1000 nm

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Colloidal Silica products

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Solid Liquid Gas

Solid Alloy Sol Aerosol

Liquid Gel Emulsion Fog

Gas Solid Foam

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The total surface area is now

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Na+ When the pH is basic,

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OH- OH- OH- OH-

• There are fewer OH- attached to the surface,

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2000 - 7000 mhos

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Silicic 5-6% Silica

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22% 26% 30%

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• Small particle binder, latex polymer

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Large Particle Small Particle

• This foundry converted from a large particle binder to a small particle

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