Theory and Practice of Nanoparticle Milling

John Sneeringer

&

José Ricardo Giacobelli

CMC do Brasil

Custom Milling & Consulting, Inc

What does a Media Mill Do?

Media milling in many industries can also be referred to as a “wet process”. There is a
transfer of energy from a rotating mechanism to the grinding beads that are also known as
media. The grinding beads will reduce particle size of solids suspended in liquid materials
(dispersions or slurries). Between the grinding of the particles and the rotation of the mill it
lowers the likelihood of re-agglomerating, settling or flocculating.

Stages of Dispersion

As the liquid and materials flow through the media they go through what we call stages of
dispersion. After different levels of energy have been applied to a mixture of solids and
liquids the objective is always to reach the finest stage of “final dispersion” with a stable
suspension of dispersed solids. (Figure 1)

Figure 1

ParticulateClum Pre-Mix Initial Shear Final

Dispersion
Importantps
Distinction in Media Milling

When you are processing liquid materials there are two distinct ways that particles are
broken down. It is important to understand the difference between dispersion and grinding
because the energy milling configuration required for each can be vastly different.

- Dispersion vs. Grinding

o Dispersion or De-agglomeration involves breaking agglomerates into their
component particles.
o Grinding involves breaking discrete particles down to a smaller sized discrete
particle

How do beads and product interact in the mill?

As the liquid flows inside of the mill it moves the beads along with it creating an interaction
between the liquid and the beads.

- A viscous “coupling” is created between the liquid/slurry/suspension and the agitated

bed of grinding media
- Because of the hydraulic nature of the system, beads of “media” must have enough
kinetic energy to disperse or grind the suspended solids, depending on the
liquid/particle characteristics

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Horizontal Media Mills (Figure 2)

- Jacketed grinding chamber

- Cartridge mechanical seal (newer technology)
- Separation devices are static or dynamic screens and static or dynamic gaps
- CMC Horizontal Media Mills have length to diameter ratio of 2:7 to 1
- Correct Materials of Construction for Abrasion Resistance and Chemical
Compatibility

Figure 2

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Mechanics (Kinetics) of Media Milling

Each Product has a “specific energy” requirement. How much energy does it take to break
the particles?

- Grinding Media Interaction – this is when particles are broken down by media
interacting with media.
- Grinding Media to Particle Interaction – particles are broken apart as the come in
contact with just the media.
- Particle to Particle Interaction – as materials flow through the chamber particles with
come in contact with other particles and break apart due to the high impact from the
velocity.
- Shear vs. Impact Milling – Shear is when particles are torn apart from the liquids
moving at different velocity. Impact is when the particles are broken down after
coming in colliding with a surface area.
- Laminar or Turbulent Flow Zones (Figures 3 & 4)

Laminar Flow Turbulent Flow

Figure 3 Figure 4

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Grinding Media & Material Selection

Examples of Different types of Media (Figures 5,6,&7)

YTZ® Yttria-Stabilized
Cerium Stabilized Zirconium Oxide
Zirconox® Ceramic
Figure 6
Figure 5

Chrome or Hardened Steel

Figure 7

Media Density (Figure 8)

Figure 8

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Media Selection Factors: “Everything Depends”

Media size continued to get smaller as the requirements for transparency, color
development, and sub-micron particles continued to get more common and more
demanding. Specialty medias became available, such as Cerium and Yttria stabilized
zirconias. These materials made it possible to create smaller, denser, and more spherical
than previously existed. The small sizes represented an extremely larger population of
beads in the same volume, providing more shear and attrition than their larger counterparts.
Below are all the things that factor into media selection:

- Bead Type (chemical composition, wear resistance)

- Bead Density (depends on product viscosity and weight per gallon)
- Bead Size (relative to starting and finish particle size)
- Bead Loading (temperature limitations?)
- Product Viscosity
- Product Density (Weight Per Liter, S.G. of the formula)
- Starting Particle Size (D99)
- Bead Size should be approximately 10X the D99
- Example: D99 = 100 microns, then Bead Size should 1.0mm (1000 microns)
- Desired Particle Size (D50)
- Bead Size should be approximately 1000X the desired particle size
- Example: D50 = 1.0 microns, then Bead Size should be 1.0mm (1000 microns)
- Grinding Discrete Particles or De-Agglomeration?
- Hardness of the Particles to be ground or de-agglomerated

Media “Spacing” at various Media Size and % Load

This chart (Figure 9) shows the “Theoretical” Media Spacing inside any mill – depending on
the Size of the Media, and the Media Load %.The Media size and Media Loading
Percentage can be manipulated to create the desired “Media Spacing” as indicated in the
chart. A smaller “Media Spacing” has the potential to yield a smaller final particle size. The
combination of Media Size and Media Load % can also be manipulated to suit the Starting
Particle Size – to handle coarse feed materials as an example.

Media Size Media Size Media Size Media Size

Media Load %
0.5mm 0.8mm 1.0mm 1.5mm

Media Spacing Media Spacing Media Spacing Media Spacing

Microns Microns Microns Microns

60% 94 151 189 282

65% 79 126 157 235

70% 65 103 129 194

75% 52 83 103 155

80% 40 64 80 120
85% 29 47 58 88

Figure 9

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 Media Size vs Population

- 2mm beads = 577,500 beads per liter

- 1mm = 4,619,000 beads per liter
- 0.5mm = 36,970,000 beads per liter
- 0.2mm = 579,700,000 beads per liter

Media Size vs. Grinding Performance

Grinding efficiencies using the different sized media are represented in the following chart.
(Figure 10) It becomes readily apparent that in certain systems, the smaller beads are
infinitely more efficient and yield a significantly smaller final particle size in a shorter amount
of time. The ability to use smaller bead sizes depends on the product characteristics, such
as starting particle size, viscosity, rheology, and specific gravity of the formulation. The
selection of grinding media size and density of the beads also depends on whether the mill is
being used to disperse/de-agglomerate fine solids, or actually grind discrete solid particles.

Figure 10

How much media is enough? (Figure 11)

- The 3 conditions of media loading are shown below: (1)Too much media - mill acts
as giant filter
- (2)Space between media right - deagglomeration will be achieved
- (3)Too little media, no work done.

Figure 11
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Particle Size vs. Energy Input

Once you select the correct media and load percentage you can begin to track the quality of
product by the energy input. If milling equipment is monitored carefully, and is properly
maintained, the total energy input can be an indicator of product quality. Energy by itself is
not a direct indicator of quality. Energy vs. Time is a direct indicator of efficiency, and can be
a direct indicator of quality and particle size. This chart shows the correlation of Increasing
Energy Input vs. Decreasing Particle Size. Generally, more energy input equals smaller
particle size. (Figure 12)

Energy Input vs. Particle size

1000
Energy Input

100

10

1
100000 10000 1000 100 10 1 0.1

Particle Size

Figure 12

Process Variables

Independent Variables Dependent Variables

• Grinding Media • Product Viscosity
• Milling Shaft Configuration • Product Density
• Milling Shaft Speed • Product Particle Size
• Product Throughput • Product Temperature
• Product Pressure
• Product Quality
• Product Throughput

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Horizontal Media Milling Processes

- Discrete Pass (single – continuous) (Figure 13)

- One Discrete Pass of material from one tank through the mill into another tank.
- If product quality is not achieved, material can be passed through the mill a
second time. However, a second clean tank is required.
- One Discrete Pass operation quality is generally 5 to 7.5 Hegman or 5 to 36
micron median particle size.
- General starting particle size is 25 to 100 micron media particle size.
- Good for viscosities greater than 1000 cps @ 100 rpm using Brookfield.
- One pass productivity is the best – if product quality can be achieved.

Figure 13

- Cascade Mode Operation (duplex or multiple pass) (Figure 14)

- When more than one discrete pass is required, then the most efficient
manufacturing process must be chosen. If the product requires two passes to
achieve the desired quality, this can be done with one mill, and multiple tanks as
indicated on the previous slide. However, this can also be accomplished with a
Duplex Mill manufactured by CMC. Two milling assemblies are built on a
common frame. The product passes directly from Chamber #1 into Chamber #2
with a continuous output stream of finished product. The product receives two
discrete passes across the mill, but the customer only handles the product one
time.
- Multiple Discrete Pass: Two Mills in “series” or two milling chambers on one
common frame.
- The concept is to operate one pass through two or more chambers.
- Larger media can be used in the first chamber with finer media being used in
successive chambers.
- The mode of operation is usually used for high volume applications and to
eliminate extra process tanks.
- Can have a starting particle size of 25 to 500 micron median particle size and can
achieve sub-micron particle size with the right selections of media.

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Figure 14

- Recirculation Operation (Figure 15)

- Recirculation Operation can be chosen for various reasons in production.
Generally, if a product requires more than two discrete passes through a
Horizontal Media Mill, then Recirculation may be a good option. This requires
less operator interface, and less equipment than two discrete passes, or a Duplex
milling arrangement.
- Very fine particle size requirements - less than 5 micron median particle size to
sub-micron
- Optimum process is premix tank > then one complete pass at moderate flow rate
into second tank and begin high flow recirculation.

Figure 15

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Recirculating Mills

- The operating concept is: “many passes, at a high flow rate”.

- Designed to narrow residence time distribution curve, and produce a narrow
particle size distribution.
- Used with agitated holding tank, mill base is re-passed time after time, until
product quality is achieved
- Lower Viscosity with good flow properties
- Almost any type of mill can be used in recirculation, but some are more flexible
and efficient than others.

Recirculation Milling

- Statistically after 4.5 tank circulations, 99.5% of the product in the tank has been
ground.
- After 10 tank circulations, 99.9% of the material has passed through the mill 1
time.
- After 22 tank circulations, 99.99% of the material has pass through the mill 1
time.
- 3 to 5 tank circulations are equal to 1 Discrete Pass

Recirculation Guidelines

- Single Tank Recirculation can be done, but this is less efficient and material must
pass through the machine an additional pass if product quality is measured from
the discharge pipe of the mill (less efficient).
- The rate of recirculation should be as high as possible – generally 1 to 2 times
the NET liquid chamber volume per minute. This equals a “Residence Time “ of
about 60 seconds on a CMC Horizontal Media Mill.
- Optimum flow rate depends on product characteristics
- It is necessary to use mixer in the tank to ensure good batch turnover (generally
turn over the tank in 60 seconds or less). If a good mixer is not used, you are
wasting your time!
- Most products require 10 to 20 theoretical turnovers to achieve the Median
Particle Size of less than 1 micron

Conclusion

There are many ways to use media mills to achieve the same quality. In conclusion you
need to consider multiple things about your operation in order to achieve the best results.

- Evaluate your product

- Evaluate your plant
- Evaluate your operators

Look at everything about your entire process to come up with what is the best process for
you. Each selection that you make will all depend on the final results that you want to
achieve. From the selection of type of media, the size of media, which processing technique
you want to use and the kind of machinery set up.

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