Aerosol

Formulation
Considerations
Robert D. Geer

2011 RSC Chemical Solutions, a Division of Radiator Specialty Company

Introduction
Frequently, formulators are faced with the challenge
of delivering an effective, quality product within a
short period of time.
Formulating an aerosol product is far more complex
than a liquid or liquid spray product. When you talk
about an aerosol formulation the entire package must
be considered, the concentrate, container,
valve/actuator, and the propellant.
Each component of the aerosol formula is equally
important and must be fine tuned to make the
product functional. The following topics are by no
means inclusive or applicable to all situations, but
can be used as a starting point.

 Topics that will be reviewed are:

Formulation Cost
Aerosol Container Types
Raw Material Selection
Formulation Types
Regulatory Issues
Container Corrosion
Fill Levels
Propellant Selection
Spray Characteristics
Stability Testing

FORMULATION COST
The most important requirement of any project is to
determine how much money is available for the
aerosol formula. Usually the only exception to this is
when the product is unique or first to market. The
pricing information will usually come from Marketing
or Sales. If your product is a knock-off, a pricing
structure for the product already exists. Focus
groups are often used by marketing to determine
consumers reaction to a new product concept and
what price they would be willing to pay.
Always use existing raw materials if possible. By
using existing inventory, better pricing can be
realized when purchasing at a higher volume. This
also helps keep the raw material inventory costs at a
minimum.

FORMULATION COST
Type of aerosol container: A non-specification can
is the least expensive. 2P or 2Q cans are more
expensive and adding a seam vent adds more cost.
Piston and barrier bag aerosol containers are more
expensive. The aerosol formulation pressure
measured at 130F will determine what aerosol
container can be used for the product.
Valve/actuator and cap: Costs are fairly uniform
with these items unless you need a non-stock or
specialty item to dispense your product such as a
360 spray valve.
Type of Propellant used: The cost of the propellant
can have either a major or minor impact on the
price of the aerosol formulation.

AEROSOL CONTAINER TYPES

Three piece and two piece metal containers (tin
plated steel)
Unlined Metal Containers: This can is used for
solvent based aerosols and used for water based
concentrates which contain corrosion inhibitors.
Lined Metal Containers: This can is used mostly for
water based applications. Solvents will usually
dissolve these linings. Water based formulations
containing over 19% Dimethyl Ether should use an
unlined can with a good corrosion inhibitor package.
Dimethyl Ether at this level will penetrate the can
lining allowing attack of the tinplate. Some of the
two piece containers only come lined, therefore
stability must be run for solvent blends.

AEROSOL CONTAINER TYPES

Double Lined Metal Containers: This can is used for
water based products where added corrosion
protection is required.
Interior coatings are normally applied before
container fabrication. Common linings are phenolic
resin, urethane, or epoxy.

Single piece Aluminum cans (lined and unlined)

Plastics containers
Glass containers (perfume)
Piston and Barrier Bag containers (gassed from the
bottom).

Raw Material Selection

It is always best to use in-house raw materials.
Review current and past in-house formulations as
a potential starting point. Dont rediscover the
wheel.
McCutcheons publishes a set of books named
McCutcheons Detergent and Functional Materials.
These are excellent references.
The Internet is very useful for gathering Raw
Material literature. Companies now have their own
websites.

Raw Material Selection

Chemical Distributors and chemical manufacturers
are an excellent source for securing information on
potential raw material components and newly
developed raw materials. One can always secure a
secrecy agreement to keep information confidential.
If you are duplicating an existing product, get
product samples for analysis and the products
Material Safety Data Sheets.
Natural or synthetic raw materials: Always be open
to new ideas. Although the cost of these materials
may be high, they may be cost effective in the
finished aerosol formulation.

Formulation Types
Water Based (Emulsions, Dispersions):
Water based products are normally contained in
lined and double lined cans ( phenolic resin,
urethane, or epoxy linings). They are also
contained in unlined cans if an effective
corrosion inhibitor is used.
Propellants normally used in aqueous products
are Hydrocarbon, Hydrocarbon Blends, Dimethyl
Ether, Hydrofluorocarbons, and Nitrogen.
The only propellant that is not normally used in
aqueous formulas is Carbon Dioxide. This
propellant in an aqueous medium will form
carbonic acid causing potential corrosion
problems and can also affect the physical
parameters of the finished aerosol product.

Formulation Types
Water Based (Emulsions, Dispersions):
Because of cost, the majority of water based
aerosols are most likely dispensed using a
hydrocarbon propellant at a 4 to 10% level.
Since Dimethyl Ether is soluble in water, if over
19% DME is required to dispense the contents, a
good corrosion inhibitor must be used because
DME will penetrate can linings allowing attack of
the tinplate. Nitrogen is less commonly used.
Corrosion Inhibitors, anti-oxidants, and biocides
are typically used in aqueous formulas.

Formulation Types
Solvent Based (Water in Oil, Dispersions):
Unlined containers are normally used because
most solvents will dissolve the interior coating of
the can.
If you have a moisture content of greater than
0.1% present in the concentrate, a corrosion
inhibitor will most likely be necessary. In
certain situations, even a moisture content less
than 0.1% could cause interior can corrosion.
Propellants used in solvent formulas are
Hydrocarbons, Hydrocarbon blends,
Hydrofluorocarbons, DME, Carbon Dioxide, and
Nitrogen.

Formulation Types
Solvent Based (Water in Oil, Dispersions)
Solvent Formulas will normally require a higher
level of the liquified gas propellant. Propellant
levels as high as 1/3 of the Net Content of the
product may be necessary to completely
discharge the can. It is normal for the DME,
Hydrofluorocarbon and Hydrocarbon propellants
to act as solvents in these formulas.
Carbon Dioxide levels in solvent formulas will run
between 2 to 7% and Nitrogen will run about
0.5 to 2%. The saturation level of Carbon
Dioxide in the concentrate is greater than that of
Nitrogen.

Regulatory Issues
DOT Regulations for Aerosol Containers
CFR, Title 49, Section 173.306
Containers of 4 fluid ounces (118.3 mL) overflow
capacity or less are exempt from the following
requirements, provided they hold non-hazardous
materials.
Liquid content of the concentrate and gas must not
completely fill the container at 130F.
Container must be capable of withstanding, without
bursting, a pressure of one and one half times the
pressure of the contents, when at 130F
equilibrium. Distortion is acceptable.

Regulatory Issues
DOT Regulations for Aerosol Containers
CFR, Title 49, Section 173.306
Container must not be used for contents with
pressures that exceed 180 psig at 130F.
DOT 2P CONTAINER: If the content pressure
exceeds 140 psig but does not exceed 160 psig
at 130F a DOT Specification 2P container is to
be used.
DOT 2Q CONTAINER: If the content pressure
exceeds 160 psig but does not exceed 180 psig
at 130F a DOT Specification 2Q container is to
be used.
Non Specification Containers require a 210 psig
burst resistance min..

Regulatory Issues
DOT Regulations for Aerosol Containers
CFR, Title 49, Section 173.306
The container must not exceed a capacity of 61
cubic inches capacity ( one liter).
Each container must be subjected to a test
performed in a hot water bath. The temperature of
the bath and the duration of the test must be such
that the internal pressure reaches that which would
be reached at 55C (130F) or 50C (122F) if the
liquid phase does not exceed 95% of the container
at 50C (122F).

Regulatory Issues
Biodegradability: Is Biodegradability one of the
product requirements? What is the definition of
Biodegradable? When referring to
biodegradability, readily and inherently
biodegradable are terms that are widely used in
industry today.

Readily Biodegradable: A material is considered

to be Readily Biodegradable if it shows a >60%
degradation within a 28 day period. Readily
Biodegradable is preferred because it does not
require a long term bio-remediation.
Inherently Biodegradable: This means that the
material will eventually degrade.

Regulatory Issues: Biodegradability

ASTM Definition of Biodegradable: They have
defined Biodegradable as a function of degree of
degradation, time, and test methodology. ASTM
D5864 describes inherently and readily
biodegradable.
Inherently Biodegradable: 20 to 60% conversion of
CO2 within 28 days. The rate of Biodegradable
Activity.
Readily Biodegradable: >60 to 100% conversion of
CO2 within 28 days. The rate of Biodegradable
Activity.

Regulatory Issues
Volatile Organic Compounds (VOCs):

It is no longer just California! A number of

Northeastern States have already adopted

legislation similar to that of the California Air
Resource Board (CARB). The OTC States (Ozone
Transport Commission-Virginia to Maine) and the
Ladco States (Illinois, Indiana, Michigan, Ohio and
Wisconsin) are making efforts to reduce air
pollution by reducing the VOCs in consumer
products.

REGULATORY ISSUES:
NEW 2003 CARB VOC LIMITS
Effective VOC Standard
Date
Automotive Brake 12/31/2010
10
Cleaners
Carburetor or
12/31/2010
10
Fuel Injection Air
Intake Cleaner
Carpet and
12/31/2010
50
Upholstery
Cleaner (Aerosol)
Engine Degreaser 12/31/2010
10
(aerosol)

REGULATORY ISSUES:
FUTURE CARB VOC LIMITS
Effective Date VOC Standard
Fabric Protectant
(non-aerosol)
Glass Cleaners
(Aerosol)
Motor Vehicle Wash
(non-aerosol)
Multi-Purpose Solvent

12/31/2010

12/31/2012

10

12/31/2010

0.2

12/31/2013

Paint Thinner

12/31/2013

Spot Remover
(Aerosol)

12/31/2010

15

Regulatory Issues
Product Hazards:
The role of the chemist is no longer to just
formulate, but to ensure that the product being
developed uses chemicals that are safe for
consumer and environmental use. If the product
will be used in the home there is a chance of
children being exposed to the product. If used in
industry, the function of the finished product may
dictate what hazardous materials are used. It is
also the responsibility of the chemist to ensure that
the product is properly labeled according to federal
and state regulations. If your company has a
Regulatory Department, they will normally handle
labeling issues.

Regulatory Issues: Product Hazards

Flammability: If you need a fast drying or
evaporating formula, then the odds are that you
will develop an Extremely flammable aerosol. The
Flammability of an aerosol is primarily determined
by a Flame Extension Test, not by flash point. It is
not feasible to run a flash point with propellant
present.
Extremely flammable contents of a self-pressurized
container means contents of a self-pressurized
container that, when tested by the method described
in Sec. 1500.45, a flashback (a flame extending back
to the dispenser) is obtained at any degree of valve
opening and the flashpoint, when tested by the
method described in Sec. 1500.43a, is less than 20
deg.F (-6.7 deg.C).

Regulatory Issues: Product Hazards

Flammable contents of self-pressurized container
means contents of a self-pressurized container that,
when tested by the method described in Sec.
1500.45, a flame projection exceeding 18 inches is
obtained at full valve opening, or flashback (a flame
extending back to the dispenser) is obtained at any
degree of valve opening.

Regulatory Issues:
FLAME EXTENSION APARATUS

Regulatory Issues: Product Hazards

Toxic: means any substance which has the
capacity to produce personal injury or illness to
man through ingestion, inhalation, or absorption
through any body surface.
Highly Toxic. These products can produce death.
An example is methanol which must be labeled
Poison with a skull and crossbones symbol and a
statement of Can not be made non-poisonous.
Corrosive: means any substance which in contact
with living tissue will cause destruction of tissue by
chemical action, but shall not refer to action on
inanimate surfaces.

Regulatory Issues: Product Hazards

Irritant: means any substance not corrosive
which on immediate, prolonged, or repeated
contact with normal living tissue will induce a local
inflammatory reaction.
Cancer/Reproductive Harm: If a product sold
in California contains a California Proposition 65
chemical, the manufacturers must add the following
statement to the product label; This product
contains chemical(s) known to the state of
California to cause cancer and/or reproductive
toxicity.
Pressurized Container: All aerosols have the
potential to explode or burst when exposed to heat,
flame, or sunlight.

Container Corrosion
Corrosion: Corrosion is not just an interior can

problem. It occurs both on the interior and exterior

of the can. Common corrosion promoters are
chloride and hydrogen ions. The presence of
chloride ions can cause container breakout within a
short period of time. Tinplate will also corrode
under high humidity conditions. Free water must
be present for this corrosion to take place.
Corrosion is a major problem that could lead to
product recalls, order cancellations, bad press, and
potential lawsuits.

Exterior Corrosion: Uninhibited hot tank water,

water left in the valve cup, or storage of the aerosol
container in a high humidity area, especially close
to the ocean, will promote can corrosion.

Container Corrosion
Crevice Corrosion: Also referred to as seam
corrosion, the weld seam, top and bottom seams.
Pitting Corrosion: Pitting corrosion is extremely
localized and an intense form of attack which can
lead to can perforation.
Stress Corrosion: This corrosion is localized at
the stress or worked areas of the aerosol can, such
as the dome chimes or valve cup bends.

Container Corrosion
Seven areas of interior corrosion:
Vapor Phase crevice corrosion
Vapor Phase corrosion
Interfacial corrosion
Weld corrosion
Liquid phase corrosion
Liquid phase crevice weld corrosion
Liquid phase weld corrosion

Container Corrosion:
Interior Corrosion

Container Corrosion
Corrosion Inhibitor Systems: Corrosion
inhibitors are formulated into the concentrate to
treat these areas of interior corrosion. It is not
unusual to use an inhibitor for the liquid phase and
one for the vapor phase. Typical corrosion
inhibitors are sodium nitrite, morpholine,
triethanolamine, and ammonia. As a general rule,
sodium nitrite and amine types of corrosion
inhibitors are not used together because there is a
possibility that the combination may form
N-nitrosamines. Corrosion is also affected by the
pH of the contents. Extreme pHs below 5 and
above 10 will commonly promote corrosion.

Container Corrosion
Even with the use of inhibitors and adjustment of
the pH, corrosion could still take place. D.I. Water
should always be used in aerosol formulations
because all traces of the chloride ion have been
removed which will promote corrosion.

Fill Levels
Aerosols are filled according to Net Weight, which
includes the concentrate and propellant. Since
aerosols can not be poured out of the container and
checked for volume, weights are used.
Head Space: This is the area between the liquid
phase and the bottom of the valve. Compressed
gases usually require a min. of 15% headspace
whereas hydrocarbon propellants usually require
less.
An Equilibrium Vapor Pressure at 130F of the
filled aerosol product will determine whether the
liquid contents needs to be reduced or a vapor
depressant is necessary.
Net Content: The aerosol container is required to
dispense the Net Weight stated on the label.

Propellant Selection
Propellants provide the power to dispense the
aerosol product. They also influence the form
in which the product is discharged and they are
either liquidified gases or compressed gases.

Hydrocarbon and Hydrocarbon Blends:

A-17: n-Butane
A-31: Isobutane
A-46: Propane/Isobutane (15.1/84.9)
A-70: Propane/Isobutane (41.9/58.1)
A-108: Propane

Properties of Hydrocarbon Propellants

Propane Isobutane n-Butane
Vapor
108 psig
Pressure @
70 F
Flash Point -156F

31 psig

17 psig

-117F

-101F

Solubility in 0.01%
water @
by Wt.
70 F
Boiling
-43.7 F
Point
Kauri15
butanol
Value

0.01% by
Wt.

0.01%
by Wt.

10.9 F

31.1 F

17

20

Propellant Selection
Hydrocarbons and Blends:
They are widely used in water based
products because they are economical.
They are not soluble in water and require a
low use level of 4 to 10% of the net content.
They provide a constant spray rate
throughout the discharge of the concentrate.
Hydrocarbon and hydrocarbon blends offer a
wide range of spray pressures to achieve the
desired spray pattern and discharge rate.
Disadvantage is their flammability with a
flash point ranging from -101 to -156F.

Propellant Selection
Dimethyl Ether:
DME is significantly higher in price than
hydrocarbon propellants.
Classified as a flammable gas.
It is a very strong and aggressive solvent.
An advantage of DME is its solubility in and
compatibility with aqueous formulas.
Disadvantage of DME is that in aqueous formulas at
levels at or above 19%, the DME will attack the can
lining thus requiring a corrosion inhibitor.

Properties of Dimethyl Ether

Vapor Pressure @
70 F
Flash Point
Solubility in Water
@ 70 F
Boiling Point
Kauri-butanol Value

63 psig
-42 F
34% by Wt.
-12.7 F
60

Propellant Selection
Hydrofluorocarbon Propellant
Major disadvantage of these propellants is their
cost.
Hydrofluorocarbons are non-flammable.
As with hydrocarbons and DME, they provide a
constant vapor pressure during container discharge.
R134a
Advantage of R134a is that it is not listed as a
Volatile Organic Compound.
Disadvantage of R134a is that it can have a
vapor pressure of over 180 psig at 130F.

Hydrofluorocarbons

Vapor
Pressure @
70 F
Flash Point

HCFC-152a

HCFC-134a

62 psig

70 psig

0F

0F

Solubility in
1.7% by Wt.
water @ 70 F

0.095% by
Wt.

Boiling Point

-11.2F

-15F

Kauri-butanol
Value

11

9.2

LIQUIFIED GASES

Propellant Selection
Compressed Gases
Advantages with the compressed gases are:
non-flammable
non-toxic
environmentally safe
inexpensive
can be used at low temperatures

Propellant Selection
Major disadvantage with compressed gases is that
over the use of the product, the delivery rate of the
aerosol formulation will drop off.
Carbon Dioxide is not used with water based
products due to formation of carbonic acid
They do offer an advantage over the liquified gases
at temperatures below 0F. Usually carbon dioxide
will loose half its ambient pressure when stored at
0F and below. Liquified gases at 0F and below
can exhibit a negative vapor pressure.

Properties of Compressed Gases

Carbon
Dioxide

Nitrous
Oxide

Nitrogen

Vapor
Pressure
@ 70 F
Flash
Point

837 psig

98 psig

None

None

None

Solubility
in water
@ 70 F
Boiling
Point

0.82

0.6

0.016

-109F

-127F

-232F

COMPRESSED GASES

Spray Characteristics
Spray characteristic are determined by the
actuator/valve/propellant and concentrate used.
Important contributors are the volume of gas used,
the vapor pressure of the propellant, the
propellant/ concentrate ratio and the solubility of
the propellant in the concentrate.
Spray Type:
Foam : Long lasting foam, quick breaking
foam, or a foam that will cling to vertical
surfaces.
Mist: A very wide circular, donut, or oval type
spray pattern. Window cleaners use a mist.
Coarse Spray: Household cleaners and tar &
bug removers will use this type of spray.

Spray Characteristics
Stream: This type of spray would be used by a
brake cleaner, choke & carburetor cleaner, or
engine degreaser.
Bead: A bead is used to deliver a mastic type
of product such as caulking compound, or a
construction adhesive used to glue the sub-floor
or drywall.
Spray Rate: How fast do you want the material
dispensed from the container? You may have a low
spray rate because only a small amount of the
material is necessary for the job whereas some
products may use a high spray rate to help achieve
their end purpose.

Spray Characteristics
The spray characteristics of the aerosol are directly
dependent upon the valve and actuator selection.
This selection is usually by trial and error. Usually
this process can be speeded up by submitting
concentrate samples to the valve/actuator
companies and requesting valve and actuator
samples to achieve your desired spray rate and
spray characteristics.

Stability Testing
There are two types of stability testing:
electrochemical testing and long term static
testing. Electrochemical testing provides a
limited amount of information but is an effective
screening tool. Long term static testing provides
the most significant information such as: weight
loss, concentrate/ propellant saturation changes
(vapor pressure measurement), maintaining
original spray characteristic, corrosion, and
concentrate stability(separation, coagulation,
chemical change, color, and odor change). Long
term static testing is normally done at a
temperature of 120F, over a period of three
months to a year.

Stability Testing
Concentrate Stability: This stability testing is
usually run in glass containers because you do not
want the container to be a contributing factor to
formulas instability.
Product and Container Stability: Once an
acceptable formulation is achieved, start stability
testing in the aerosol can, valve, dip tube, and
gaskets.

Stability Testing
Concentrate and Propellant Stability: It is
always best to prepare an adequate number of
samples so that at least one sample can be tested
every week for the first three months, then tested
every month depending upon the time allotted for
stability testing. Weekly tests should be made at
ambient temperatures. Testing will involve:
Weight loss
Pressure testing
Spray rate, spray pattern
Evacuation of Net Weight
Concentrate color and odor
Open aerosol container and evaluate for corrosion
and dip tube condition.

Stability Testing
Also at least one test sample of the concentrate and
propellant should be prepared in a pressure
reaction vessel (glass aerosol bottle). With the use
of a glass aerosol bottle, it is easy to view whether
the product separates and mixes back into solution.
A shake well before using may be required on the
label directions. Also you can look for color and
volume changes in the container which will affect
the the vapor pressure, thus affecting the spray
characteristics.

Low Temperature Stability: If the product is

not freeze-thaw stable, directions such as protect
from Freezing needs to be added to the product
label.