3M BRAND
FLUOROCHEMiCALSURFACTANTS
FC-95, FC-98~ FC-128~ I:C-134, I:X-161~
FC-170, FX-172

Exhibit1042
State of Minnesota v. 3M Co.,
Court File No. 27-CV-10-28862

3MA01201629

1042.0001

CONTENTS

Introduction
Surfaces or Interfaces
Surface Tension
Sur factant s

Fluorochemical Sur factants
Measurement of Surface Tension
Characteristics of 3M Brand Fluorochemical Surfactants
Solubility of 3M Brand Fluorochemical Surfactants
Handling and Use
Surface Properties
Introduction
Surface Tensions in Water
Surface Tensions in Acids
1. Hydrochloric Acid
2. Nitric Acid
3. Phosphoric Acid
4. Sulfuric Acid
Surface Tensions in Alkali
1. Potassium Hydroxide
2. Sodium Hydroxide
Surface Tensions in Other MediaInter facial Tension
Emulsific ation
Foaming Power
Wetting Power
Applications of 3M Brand Fluorochemical Surfactants

Introduction
Guide to the Selection of 3M Brand Fluorochemical Surfactants
Cleaners
I. Alkaline Cleaners
2. Bottle Cleaners
3. Concrete Gleaners
Corrosion Inhibit0rs - Corrosion l~esistant Films
i. Corrosion Inhibitors - General
2. Ste el
Protective Coatings
3.
Dips, Etches, and Strikes
i. Aluminum Bright Dip
2. Copper and Brass Bright Dips
3. Aluminum Acid Etch
4. Aluminum Base Etch
5. Magnesium Etches
6. Copper Strikes
Electrolytic Processes
I. Chrome Plating
2.

Nickel Plating

3. Electrochemicai Milling
Evaporation Inhibition
Organic l~eactions
i. Hydrolysis
2. Sulfonation
Paper Pulping

3MA01201630

1042.0002

CONTENTS (¢ontinced)
Pickling or Descaling
1.
Steel
2.
Stainless Steel
Spring Steel3.
Resins and Plastics

Solvents~" at e r Treatments

Open Cooling Water Systems
Closed Heating Systems
Waxes

I.
2.

.~I!~sdine Systems"Lock and Key" Systems

Toxicity
Bibliography

3MA01201631

1042.0003

3M Brand Fluorochemical Surfactants

TITLE:

Date Issued :Supersedes Issue of:June 15, 1963
Y-ISTDINTRODUCTION

Surfaces or Interfaces
Oil and water do not mix, hence, there is a boundary between them.
These boundaries, known as surfaces or interfaces, exist between liquids

and liquids, liquids and solids, solids and solids, solids and gases, andliquids and gases.

solid-sosinterfaceliquid-gas interface

liquid-solidinterfaceluid-liquid interface

Surface Tension
Liquids often behave as though there is an elastic skin stretched on
their surface, A water glass, for example, can be filled to a point where thewater level is above the rim of the glass, or a needle can be floated on thesurface of the water.

The strong "elastic membrane" or high surface tensionof the water makes these effects possible.

If you were to add a detergent to

IMPORTANT NOTICE TO PURCHASER: All statements, technical information and recommendations contained heroin are based on tests
we believe to be reliable, but the accuracy or completeness thereof is not guaranteed, and the following is made in lieu of all warranties,
express or implied:Seller’s

and nmnufacturer’s only obligation shall be to replace such quantity of the product p,av~d to be defective.

Neither seller

nor manufacturer shall be liable for any injory~ loss or damage, direct or consequential= arising out of the use of or the inability to use theproduct.
Before using, user shall determine the suitability of the product fat his intended use, and user assumes all risk and liability
whatsoever in connection therewith.
No

statementor recommendation not contained herein

shallhave any force or effect unless in an agreement signed by officers ofseller and manufect umr ¯
Since the manufacturer of the product described in this technical data sheet has no means of
by
the

the

consumer or user,

purposes forwhich

it is the responsibility of thethe productmay be fit andontrolling the final use of the productimmediate purchaser and any intermediate seller or sellers In inform the user ofsuitable and of the properties of the product, including the precautionary measures

which must be taken in order to ensure the safety of the user and of other third persons and property.

WARNINGI

Do not take internally. Avoid breathing dust. Wash thoroughly after handling,

3MA01201632

1042.0004

Surface Tension (continued)

the water, the glass could not be filled above the rim and the needle would
not float. The elastic skin loses its strength; the water becomes wetter;its surface tension is reduced. Measurements of surface tension are, therefore, able to compare the effectiveness of compounds to concentrate at thesurface and so effect the properties.
Surfactants
Any material capable of reducing the surface tension of a liquid is asurfactant, or surface active agent. In the illustration above, a detergent
reduced the surface tension of water. Hydrocarbon detergents are excellent
surfactantsandare capable of reducing the surface tension of water from72 dynes/crn, to 30-35 dynes/ca. These materials are commonly used inmany processes such as washing clothes and dishes, emulsifying componentsof paint, industrial cleaning and etching, textile dyeing, and countless otherapplications.
Fluor ochemical Sur factants
A fluorochernical surfactant contains a completely fluorinated tailand solubilizing group. These compounds are capable of reducing thesurface tension of water from 72 dynes/crn, to 15-20 dynes/crn. Like thehydrocarbon surfactants, they are also active at all interfaces.

The difference between hydrocarbon and fluorochemical surfactants isfurther illustrated by concentration requirements. IV[inirnnurn surface tension
reduction of hydrocarbon surfactants (30-35 dynes/ca. ) is generally achievedat concentrations of 0.1- l~o by weight; while fluorochemical surfactants canachieve a minimum surface tension (15-20 dynes/ca. ) at approximately
0.0i% by weight (i00 parts per million).
Determination of Surface Tension
Surface tensions can be measured in any one of a number of ways.

Capillary Rise_: This method is the oldest, going back to Leonardo deVinci. When a vertical capillary is immersed in a liquid which wets
it, the liquid rises to a height, h, which is inversely proportional to
the surface tension.

tcapillarytube

4-3MA01201633

1042.0005

Determination of Surface Tension (continued)

The internal radius of the capillary tube, density of the liquid, andthe acceleration due to gravity must also be known. Exact measurements of height and radius of the capillary are extremely difficult;hence, accuracy of the method is limited.
Drop Weight: The weight of a drop which falls from a capillary tube
is proportional to the surface tension of the liquid and the radius of
the capillary. Instruments currently available, called drop-counter.<and stalagmometers, are based on this principle. A serious disadvantage of the method exists, however, in that drops must be formed very
slowly, only one in every several minutes. This measurement is neither
accurate nor rapid.
P~upture of the Surface. "Tensiometer": Probably the fastest and mostreliable method of surface tension measurement is the pull-ring methodby duNouy. The procedure measures the "tension" or pull required toc&use a ring to break free from the liquid surface. The tensile force is
proportional to the surface tension.

ring
liquidThe accuracy of the duNouy Tensiometer is especially great if liquids
having similar properties are compared. It is also a fast procedure,
capable of measuring surface tension of rapidly aging systems.
Platinum rings are used; hence, clean-up between measurements is
simplified over the capillary methods.

Additional information on surface tension measurements is found in the
bibliography references (I, Z). The extremely low surface energy of thefluorocarbon tail is also discussed (5, 4).

3MA01201634

1042.0006

CHAI<.~CTEP~ISTICS OF 3M BRAND FLUOROCHEMICAL SURFACTANTS
The main features which distinguish these materials from conventionalsurfact~nts are as follows:i.

Stabilitya.
Chemicalb.

Thermalc.

Biological

Several are stable in 90% H202, anhydrous
hydrazine, hot concentrated mineral acids,
and alkalis.
Certain members of this family are stable
up to 750°F.
-

Some are completely resistant to biologicalattack.

Surface Activitya.
Aqueous Systems- Capable o.f surface tension reduction,
I0-I 5 dynes/cm, lower than conventionalsurfactants.
b.

Organic Systems - Many 3M surfactants are active in organic

systems, causing reductions in the surface
tensions of organic solvents.
c.

Wetting-

Wetting of materials can be greatly improved.
Or, a variety of substrates can be madehydrophobic and/or oleophobic.
d.

3.

Foams

-

Stable, long-lasting foams can be produced
in media which would be destructive toconventional surface active agents.
Low
foaming materials are also available.

Efficiencya.

Economical

Effective at extremely low concentrations,frequently .at 50-100 parts per million

or less.

3MA01201635

1042.0007

SOLUBILITY OF FLUOI~OCARBON SURFACTANTS

SOLUBILITY
I000 Grams of Solvent,Grams Surfactant per

SOLVENT

FC-95

FC-98

FC-128FC- 170

FX- 172

AcetoneBenzene

I00
0.8

20
0.2

Z
0.2

> I0
0.6

> I000
2

600
500

i000
1

chloride
0.04
Z
Ethyl Alcohol
Heptane0.03
Isopropyl Alcohol 3
Isopropyl Ether 0.1
Methyl Alcohol
60
Perchloroethylene
0.07
Toluene
1
2
Water

0.04
Z0
0.09
30
0.3
40

0. 1
10
0.03
8
0. Z
60

Nil
100
Nil
10
0.04
80

0.8
80
0.7
> 1000Z070

470> 10007> 1000250> i000Z> 10001> 100015> i000

0.09
0.9.
10

0.2
0.1
200
(gel)

0.04
0. 1
>5
(gel)

0.7
1
I0

690
550
> 300
(gel)

i00
I0
> 500
(Foam)

FC-134

FX-161

Carbon Tetra-

Procedure Used Above: Saturated surfactant solutions were equilibrated andfiltered. Solubilities were determined after evaporation of the solvent.

SOLUBILITIES IN ACIDS AND ALKALIHydrochloric acid, . 1
Hydrochloric acid, 37%
Nitric acid, 1
Nitric acid, 70°/o
Phosphoric acid, 1 1
Phosphoric acid, 85%
Sulfuric acid, 1 2½%

Sulfuric acid, 97%
Potassium hydroxide,

FC-95

FC-98

FX-161

1
0. I
1

<10

< 0.01< 20< 0.01~ i0< 0.01

>5
>I
>i
I0
0.5

20%

3MA01201636

1042.0008

HANDLING AND USE

The solubilities of the 3M Bra~nd Fluorochemical Surfactants inaqueous and organic media are usually lower than those of conventionalhydrocarbon surfactants. Although the solubility limits of a given 3M
surfactant in water may be 0.1% or less, this is not necessarily restrictiveof its capacity to function effectively. However, the surfactant must havesome solubility in a system if it is to be effective. Surface tension should
be checked when solubility is in question, to determine whether or not thematerial is actually present in adequate levels to affect surface propertiesof the system significantly. Examination for color change and foaming
can also be used as guides to indicate adequate solubility. In the case of
surfactant use as a priz~ary emulsifier, addition levels higher than 0.1%
are usually required. Their use as secondary emulsifiers or stabilizers
may not require use levels greater than this.
Where solubilities are not sufficient to achieve results in a particular
media, it is recommended that the use of cosolvents be investigated. In
many cases this will mean the addition of only a few percent of a cosolvent(or cosolvents) to form a binary or ternary system. For example, theaddition of 5% acetone or isopropanol greatly increases the solubility ofmany fluorochemical surfactants in water. Similar examples occur withorganic systems.

Because of low solubilities, 3M Brand Surfactants may be slow todissolve. The use of heat will greatly increase solution rates and isrecommended whenever possible. In some cases, pre-dissolving thesurfactant in a small amount of a compatible solvent in which its solubility
is large will greatly facilitate its solution. In such cases, very little ofthe pre-solvent will be needed; in fact, simple wetting out of a solid surfactant
will often serve to increase its rate and degree of solution. It should beemphasized that :Wherever possible, the surfactant should be added to a liquid
system in a compatible liquid form. (This will insure that all of thesurfactant which has been added is being utilized. )The following is intended as a guide to helpful cosolvents for various
3M Brand Fluorochemical Surfactants.

SURFAC TANTCOSOLVENTS FOR
WATER SOLUTIONSCOSOLVENTS FORO RGANIC SO LU TIONS

FC -95
FC-98
FC - 128

Acetone orMethanol
Acetone or
Is opt opanol
Acetone
Methyl cellosolve orDimethyl formamide
Acetone or
Is opt opanol
None required’50:50 CCl4:methanol or
50:50 acetone :isopropanol

FC -I 34
FX-161FC- 170
FX- 172

Acetone or
Is opr opanolSame as above

Carbon tetrachloride
Same as FC-95
TolueneAIc ohol
AcetoneI s opr opanol-8-3MA01201637

1042.0009

SURFAC E PROPERTIES

Surface tension zmeasurements are included to show the effect Of 3M]Stand Fluorochemical Surfactants in water, various acids, alkalis, andother media.

Generally speaking, lowered surface tension values imply better
wetting properties of the surfactant solution. This is true for many ofthem in many media. However, some of these surfactants are very capableof preferential absorption on many surfaces which, in effect, would decrease the wettability of that surfactant solution to that particular surface.
An example of this diverse effect is the use of Fluorochemical Surfactants
in hydrochloric acid. FC-95 will cause a great increase in the rate of ’attack of HCI on aluminum, while FX-161 can actually stop the corrosionof aluminum by formation of a tenacious monomolecular corrosionresistant barrier film on the aluminum. It should be emphasized that thesurfactant effects just described are very selective.. The solvent,surfactant, and substrate are dependent upon one another. Our laboratories
will be pleased to assist in the selection of the proper fluorochernicalsurfactant for problem applications upon receipt of complete informationon the system and the effects desired.
Unless stated to the contrary, all surface tension data presented
were obtained with a duNouy tensiometer on solutions which had aged
16-24 hours prior to measurement.
(See introduction)

SURFACE TENSIONS IN WATER

Figure 1 compares surface tension vs. concentration of 3IV[ Brand
Fluorochemical Surfactants in water. It should be noted that extremely
low concentrations of FC-I 54 and FC- 170 give remarkably low surface
tensions in water. For example, 0. 001% (parts per million) F6-134
reduces the surface tension of water from about 72 dynes/centimeter toabout 24 dynes/era.
Figure 2 represents the effect of temperature on the surface
tensions of FC-1 Z8 and FC-134 solutions; each at concentrations of 0.1,
0.01, and 0. 001 (1, 000, 100, and 10 ppm respectively).

-9-3MA01201638

1042.0010

SURFACE TENSION, 25°C., DYNES/CM.
o

o

-10-

3MA01201639

1042.0011

SURFACE TENSION vs. TEMPERATURE OF FC-128, FC-134
IN WATER

4O

TEM PERATU RE, °C.

-11 -3MA01201640

1042.0012

SURFACE TENSIONS IN ACIDS

The stability of certain 3M Brand Fluorochemical Surfactants tostrong mineral acids provides a unique means of reducing surface
tensions of these highly corrosive chemicals. Certain of the fluorochemical surfactants are extremely stable in these acids even atelevated temperatures, and are often the only ma[erials which provide
surface activity in these media.

The effectiveness of materials such as FC-95 and FC-98 inreducing surface tension of acidic media is in marked contrast to theireffect in water. The importance of solution pH is, therefore, not to beoverlooked. Both solubility and activity are dependent on pH, thepresence of other dissolved salts, etc.

i.

Hydrochloric Acid

1
Curves for FC-95 in iZ~%,
Z5%, and 37% hydrochloric acid arefound in Figure 3. Note that minimum surface tension is attainedat from 50 to I00 ppm (.005-0.01%) FC-95.

-IZ-

3MA01201641

1042.0013

SURFACE TENSION, DYNES/CM
o

9

~0
0
0

-13-

3MA01201642

1042.0014

Nitric Acid

Figure 4 presents surface tension vs. concentration curves for
FC-95 in IZ½, Z5, 50, 70, and 90% HNO3. Bar charts are included
showing the effect of FC-95 and FC-128 in white fuming nitric acid.
The area at the left of the bar chart indicates the surface tensionof the pure acid.

-14-

3MA01201643

1042.0015

SURFACE TENSION, DYNES/CM
o

o

o

o

Z

m

-15-

3MA01201644

1042.0016

3.

Phosphoric Acid
Curves indicating the effect of FG-95 in IZ½, ZS, 50, and 85%

H3PO4 are given in Figure 5.

Note that minimum surface tensions

are achieved at concentrations of 50-500 ppm (0. 005-0.05g0)FC-95.

-16-

3MA01201645

1042.0017

SURFACE TENSION, DYNES/CM.
o

o

o

o

o

I!11

9

17-

3MA01201646

1042.0018

4.

Sulfuric Acid
IV[any 3M Brand Fluorochemical Surfactants show excellent

surface activity in sulfuric acid as shown in Figure 6.

Curves of

surface tension vs. concentration are given for FC-95 in IZ½,

25,50, and 97% HzSO4, for FC-98 in Z5% H2SO4, for FC-134 in 30%
HzSO4, and for FX-161 in 10% H2SO4.

By way of comparison, thesurface tensions of the pure sulfuric acid solutions are given in theupper right-hand corner.

-18-

3MA01201647

1042.0019

SURFACE TENSION, DYNES/CM.
c)

III

-I

0 .
~ o

0

-19 -

3MA01201648

1042.0020

In acid media it is often possible to observe an even lower
surface tension with time.

The following table illustrates this effect.

FC-1 34 in 30% Sulfuric Acid vs. Time

Concentration of FC- 134%

0. 1

0.01

0.001

0. 0001

Freshly mixed

15.2

16.4

Z4.4

71.9

After 48 hrs. standing

15.5

16.0

16.8

29.4

After 48 hrs. standing
plus heating 16 hrs. @78°C.

14.1

Z4.5

SURFACE TENSIONS IN ALKALI_S

3M Brand Fluorochemical Surfactants show excellent surface
tension reduction at low concentrations in alkaline systems.

Potas sium Hydroxide
Curves for the effect of FC-95 in I0 and 25% KOH are given in Figure 7.

- Z0 -

3MA01201649

1042.0021

SURFACE TENSION, DYNES/CM

9
/-

6
O[

- Z1 -

3MA01201650

1042.0022

Sodium Hydroxide
Surface tension vs. concentration curves are presented in Figure 8
for FC-95 in 10 and 25% NaOH and for FC-98 and FC-128 in 25% NaOH.
Bar charts illustrate the effect of other surfactants in 10,
NaOH.

40 and 50~0

The bars at the left indicate the surface tension of thesolution without surfactant.

3MA01201651

1042.0023

SURFACE TENSION, DYNES/CMo0

3MA01201652

1042.0024

SURFACE TENSIONS IN OTHEP~ MEDIAThe following bar chart, Figure 9 presents data on surface tensionsof a variety of media containing fluorochemical surfactants:
10% Acetic acidZ.

20% Calcium chloride

3.

95% Hydr azine

4.

30% Hydrogen Peroxide (at 18 C.)

5.

50% Lithium Bromide

6.

20% Sodium ChlorideoEffectiveness and stability in such rigorous media as hydrazine andhydrogen peroxide is an important characteristic of these versatilesurfactants.

- Z4 -

3MA01201653

1042.0025

o.~ FC-128

i i i i i i i i i ~i i i L_
Z

Z

100

8O

6O

5~D

40

30

20

10

"IAIO/Bq NA(] ’NOI£Nql :~ov.~a ns- 25 -

3MA01201654

1042.0026

SUP~FACE TENSION REDUCTION IN DETERGENTS

FC-1 34 effectively reduces the surface tension of a commercial
dishwashing compound (0.8% in water at 145°F. )as noted below:

FC-I 34 CONCENTRATIONSURFACE TENSION,
dynes/cm.

0 (control)

30. 3

O. 00221.0

0. 00316.2

0. 005

14.2

A comparison of these values with points on the curve of FC-134 in water,
Figure I, indicates a slight synergistic effect between the two compounds.
INT ERFAC IAL TENSION

The interracial tensions between acids and organic liquids can begreatly reduced with FC-95. For example, the interfacial tensionb~tween concentrated hydrochloric acid and an organic ester, tributyl
aconitate, was lowered from 12.6 to i. 8 dynes/cm by the addition of
0.5% FC-95 to the acid phase. Figure 10 illustrates the effect of
FC-95 on the interfacial tension between n-decane and dilute sulfuric
acid solutions of various strengths:

FIGURE 10
INTERFACIAL TENSION OF DEGANE-DILUTE SULFURIC ACIDSOLUTIONS CONTAINING FC-95

MOLAR CONCENTRATION OF SULFURIC ACID SOLUTION- Z6 -

3MA01201655

1042.0027

EMULSIFIG ATION

Fluorochemical surfactants are effective emulsifiers. However,
it is usually necessary to use concentrations equal to those required forhydrocarbon surfactants which often imposes an economic restriction
on their use. Those applications which are destructive to conventionalsurfactants by heat or chemical attack are excellent areas for the useof the fluorochemicals as emulsifiers.
Synergistic effects are often encountered when fluorochemical
surfactants are used in addition to conventional hydrocarbon emulsifier
blends. Effectiveness at considerably lower total surfactant concentration
is often realized.

Many vinyl polymers have been prepared by emulsion polymerization
utilizing fluorochemical surfactants as the emulsifiers (see U. S. Patent2, 559,752). It has been demonstrated that significantly lower emulsifier
concentrations may be used when fluorocarbons are used instead ofhydrocarbon emulsifiers.
FC-IZ8 and FC-170 are used to advantage for emulsifying liquidsof low surface energy (silicones and fluorocarbons). An homogenizer isgenerally required.

FX-17Z is an excellent stabilizer for latexes.
In applications where wetting is required, but where emulsification
is not desired, fluorochemical surfactants should receive first consideration.
Here, the normal, very low concentrations are used to provide excellent
wetting with a low degree of emulsification.
FC- 170 is also used to break cetain emulsions.

- 27 -

3MA01201656

1042.0028

FOAIVilNG POWER IN WATER(Ross-Miles Test, ASTM Method D i173-53).

SU RFAC TANTCONCENTRATION,%TEMPERATURE,
°C

FC-95

O.5
0.5
0. I
0.1

-25
50
25
50

126
169
I0
103

65
97
4
17

0.5
0.5
0. i
0. i

Z5
50
25
50

gI3
Z59
188
23Z

Z07
Z33
185
ZI0

0.01

25

iz

6

0.01

50

15

7

0.5
0.5
0. i
0.1
0.01
0.01

25
50
25
50
Z5
50

164
232
87
159
9
14

164
222
86
149
9

FC-134

FOAM HEIGHT, ram.
Immediate After 5 Min.

FC-134 forms remarkably stable foams which, in some cases, will
last for several hours. FC-95 gives foams especially stable in basic, media.
FC-95 and FC-98 give stable foams in acids. Foams in certain organic

solvents can be formed by FC-134. FX-17Z is excellent in strong acids(producing very stable "dry" foams) and in neutral aqueous media.
Although in many cases the foams produced by fluorochemical sur-factants do not appear as good as foams produced by conventional surfactants,
they have a demonstrated stability to heat and chemicals which makes theminvaluable in these applications. Users of fluorochemical surfactants in
foams have noted that many "unhealthy" looking foams were outstandingly
effective in their applications.

Defoamin£ of certain organic systems is possible through the use of
FX-161 and FC-170.

-

3MA01201657

1042.0029

FOAMING POWER IN OTHER MEDIA

Foams produced by many surfactants are sensitive to water hardness
and pH of the solution.

These conditions have been tested with FC-128

where it was found that FC-128 produces its maximum foam at a pH ofabout I0.

As the pH decreases, the foam does also.

At a pH of 7 or

below, little or no foam is produced.

Hardness in water also reduces the foams in FC-128 solutions.
This factor is easily overcome by the use of water softening or sequestering agents.

WETTING POWER IN WATER(Draves-Clarkson Test - Reference:

American Association of Textile

Chemists and Colorists Technical Manual and Yearbook).

SURFAOTANTCONCENTRATION,TEMPERATURE,

SINKING TIME

%

°C.

sec.

FC-95

0. I
0. i
0. I

25
50
70

over 300
24
35

FC-128

0
0
0
0
0
0

1
1
1
05
05
05

25
50
70
25
50
70

52
13
7
223
30
19

FC-134

0.05
0.05

Z5
70

over 300
Z5

FX-172 and FC-170 also show excellent wetting power. FX-172 issuperior to FC-128 and FC-134 and considerably better th~n FX-161 andFC- 170 in the wetting of fabrics at the 0.05-0. i% level.

- Z9 -

3MA01201658

1042.0030

APPLICATIONS OF 31M BRAND FLUOROCHER[ICAL SURFACTANTS

New uses for this class of industrial surfactants are continually
being found. Examples of their diverse applications are presented below.
These commercial products will continue to find additional problems
which they can so.effectively and economically. In this respect they
are augmented by a ,~owing list of experimental laboratory fluorochemical surfactants ~hose structures are specifically designed for aneven wider area of Consumer applications. A request to our laboratories
with full particulars as to the system involved and effects desired will
result in recommendations of the experimental or production fluorochemical
surfactants most likely suited to your application.
The highly specific nature of these materials makes any generalizations
regarding their use extremely difficult. The "Guide to the Use of 31V1 Brand
Fluorochemical Surfactants" on the following page lists the most important
properties of each commercial product. The major outstanding characteristic of each product is underlined for emphasis.
It should be added that in comparative evaluations of these materials,
it is frequently observed that one surfactant performs best in one test
while another is definitely superior in a different effect.
It is then very
advisable to evaluate surfactant blends.
These blends provide the major

effects required and, synergistically, can often show performance vs.
concentration characteristics superior to either surfactant alone. These
effects are available with blends of fluorochemical surfactants as well aswith hydrocarbon/fluorochemical surfactant blends.

- 30-

3MA01201659

1042.0031

0
o

0
o

0

~N
~0

O~
~

O0
O0

~

- 31 -

3MA01201660

1042.0032

C LEANERS

FC-98 possesses outstanding surface activity in highly alkalinesystems. Concentrations as low as 0.00Z% (Z0 parts per million) incaustic at 50°C. result in surface tensions of 30 dynes per cm. FG-95
and FC-IZ8 are similarly effective.

I.

ALKALINE C LEANERS..
Commercial alkaline cleaners are highly selective and specific in
their cleaning action. The high chemical stability and surface activityof the fluorochemical surfactants offer a new approach to improving theefficiency and broadening the selectivity range of these alkaline cleaners.
The following formulation is typical of an effective alkaline cleaner
used to remove paint and other deposits from steel:sodium hydroxide
FC-128Temperature : 180°F.
5%O. 01%The use of FC-IZ8 in the cleaner requires half the immersion time anddoubles its effective life.
An alkaline cleaning bath used on missile_products uses iZ ppm
FC-IZ8. Cleaning speed is increased substantially at lower cost thanthe previous systems.

BOTTLE CLEANERS
These are used primarily where removal of aluminum labels isnecessary. FC-98at5ppm is superior to FC-95 primarily due to therequirement of supplying the cleaner in a concentrate form containing
50% iNaOH + 5% gluconic acid. FC-95 is not sufficiently soluble to be
used in this concentrate.

3.

C ONCI~ETE CLEANERS

Phosphoric-hydrochloric acid concrete cleaners show improved
wetting of oily surfaces when FC-134 is used at levels of 25-100 ppm.

- 32 -

3MA01201661

1042.0033

CORROSION INHIBITORS C(~RROSION RESISTANT FILMS

It has been found that 3M Brand Fluorochemical Surfactants act as
corrosion inhibitors in various metal-acid systems.
They may be used asadditives to the acid media or they may be applied as a thin, protective filmon the metal prior to contact with the acid. In some cases, they exhibita pronounced synergistic effect with organic corrosion inhibitors.

I.

CORROSION INHIBITORS - GENERAL

Examples of corrosion inhibiting power of fluorochemical surfactants
as shown in following data:
CORROSION RATE,MILS PER YEARSYSTEM
304 Stainless steel in 10% hydrochloric
acid at 1B0°F.

175

Same, with 0.01% FC-134

21

Aluminum in 2N (7%) hydrochloric acidat 75°F.

1410
190

Same, with 0.01 FC-134

From the above, the effectiveness of FC-134 in reducing corrosion ofaluminum and stainless steel in hydrochloric acid is evident.
The importance of inhibitor concentration and its means of additionis illustrated in the following data:
CORROSION RATE,MILS PER YEARSYSTEMi 100 Aluminum in 10% hydrochloric
acid at 75°F.
Same, with 0.07.% FX-161 ¯ "Same, with 0. Z~o FX-161 ¯Same, with 2.0% FX-161 ~;

2320
710

2O4
Z64

STEEL
A very smooth etch is obtained when FC-95 is used in conjunction
with thio-urea or ethyl mercaptan as a corrosion inhibitor for cold rolled
steel in 5~/0 HzSO4. A synergistic effect is observed with ethyl mercaptan

and FC-9 5.
The following table lists corrosion rates, in mils per year, forthe various systems.

# FX-161 added as 10% solution in acetone¯ ~ No cosolvent used. FX-161 was not all being utilized- 33 -

3MA01201662

1042.0034

2.

STEEL (continued)

INHIBITION OF CORROSION ON COLD ROLLED STEEL BY 5% HzSO4
AT ROOM TEMPERATURE

Inhibitor

CORROSION RATE
0-4 hrs.
0-146 hrs.
456

None
O. 5% FC-95
0. 01190 Thiourea
0.011% Thiourea + 0.5% FC-95
0.093% Ethyl mercaptan

275

0.09 390 Ethyl mercaptan + 0.5% FC-95
3.

. MILS PER YEAR
146-1035 hrs.

8.8
8.1
4.9
5.0

15.6
12.5
13.4
i.I

PROTECTIVE COATINGS

Properly applied, FX-161 and FC-I 34 will improve the tarnish resistance of many metals exposed to corrosive environments as long as
flushing conditions do not prevail. These films have oil and water repellency and resistance to fingerprinting. On sealed, anodized aluminum,
increased salt spray resistance results, and 3% hydrochloric acid will
not attack the surface. Similar effects have been noted on other metals
including steel, brass, and copper. An effective procedure for preparationof these thin films is described below:_
FX- 161 on Aluminum
FX-161 is best applied to aluminum from acetone, alcohol,
alcohol:water, or acetone:water solutions. Usually 0.5-2.0% solutions of
FX-161 in isopropanol, ethanol, or acetone suffice to assure uniform coat ings in single immersion dips of 10-30 seconds.

The aluminum to be dipped should first be cleaned and degreased
completely (so that no water break is noted). Common xlegreasing solvents
followed by a dip in dilute base and a complete flushing rinse will properly
prepare the surface. Abrasive cleaning with "SCOTCHBRITE" following
the degreasing is also recommended.
Slow removal of treated pieces from the bath will insure almost
complete drainage. It is often possible to observe during withdrawal thatthe bath no longer "wets" the piece. Pieces should immediately be given
a quick rinse in distilled water to remove any excess solution which, upondrying, might cause spotting. Heating the metal after treatment often improves the permanence and tenacity of the film.
The presence of the film is easily detected because of the autorepellency of the bath (it no longer "wets" the metal) or by placing a dropof mineral oil on the surface. The drop ahould "bead up" showing a contact
angle of 45° or more.

- 34 -

3MA01201663

1042.0035

/ / /7/ / ///Wetti n8

Contact Ansle, 8/

N on-wetti ng

Note that where wetting occurs, the contact angle, 8, is very small. A
drop exhibiting non-wetting has a large contact angle and there is notendency for the drop to spread.
FC-134 is applied in the same manner from the same solvents or from
acidified water. It provides good tarnish resistance for copper and brasseven in the presence of high humidity and HZS or SO2.
Fingerprint and soiling resistance are also improved.

- 35-

3MA01201664

1042.0036

DIPS, ETCHES, AND STRIKES

Unusual effects are frequently observed when the fluorochemical
surfactants are included in etches, strikes, strippingsolutions, anddips utilized to achieve matte, or bright finishes, and the like. Sucheffects may include either accelerated reaction rate, inhibition ofreaction, improved appearance and uniformity of attack, protection fromstaining after dipping, and development of water repellent surfaces.
1.

ALUMINUM BRIGHT DIPS

FC-95 in a concentration of 0. 005% (50 parts per million) causes anincrease in the reaction rate of conventional phosphoric-nitric acid-based
aluminum bright dips.

REACTION RATESTREATMENTmg per sq. in. per 15 sec.

Aluminum in 90% phosphoric acid + 10%
nitric acid at 170°F.
Same, with 0.005% (50 ppm) FC-95

11.7

Improved brightening is imparted.
Due to the formation of a layer offoam at the bath surface, the mist and spray normally associated withthese baths is eliminated.

FC-98 has a similar effect in these dips in the 25-50 ppm range.
Increased reaction rate, improved brightening, and reduced drag-out losses
OCCUr ¯

FC-134 and FX-161 are useful in i0-15% hydrochloric acid bright dipsfor aluminum. Here, however, reaction rate is sharply reduced allowing
very smooth, blue-bright finishes on aluminum alloys which would normallybe spotty after such a dip. (See Corrosion Inhibitors.)
2.

GOPPEP~ AND BRASS BRIGHT DIPS

FC-134 and .FX-161 produce brighter finisheg with reduced drag-out
and improved stain resistance when incorporated into a 50% sulfuric
25% nitric, trace hydrochloric acid, copper bright dip solution. Superior
fingerprint resistance and a lo~°er degree of staining in nitrous oxide fumes
is imparted when the final rinses contain 0.05-0. i% of the sarn_e__surfactant.
plus 10-20% alcohol.
Similar advantageous effects are obtained with brass:

REAC TION RATETREATMENTmg per sq. in. per 30 sec.

Brass in 50% Sulfuric acid + 25% Nitricacid at 75°F.

7.8

Same, with 0.02% FX-161

9.5- 36 -

3MA01201665

1042.0037

Z.

COPPER AND BRASS BRIGHT DIPS

(continued)

Drag out losses were reduced 25% and the brass was brighter after treatment
with the bright dip containing 0.02~0 (200 ppm) FX-161.
3.

ALUMINUM ACID ETCH

Smoother etches are obtained in a 15% hydrochloric acid system at150-180°F. when 0.01% FC-134 or FX-161 is used. The reaction rate is

reduced. (See Corrosion Inhibitors). The same quantities of FC-95 or
FC-98 will sharply raise the rate of etch. If this is desired, FC-98 ispreferred since FC-95 can cause blackening.

4.

ALUMINUM BASE ETCH

FX-161 and FC-134 can be utilized in 2% sodium hydroxide to alter
etching rates. For example, at 75°F 0.01% FC-I 34 will reduce the rateof attack about 10g0 while 0. 0290 FX-161 can increase this rate by 0-2070.
Due to the speed of reaction, little or no increase in rate is observed
during a short etch with FX-161. A longer immersion is required to show
the 2090 rate increase. The use of either surfactant will reduce surface
tension of the bath which should result in reduced losses due to drag out.
5.

MAGNESIUM ETCHES

In a Z0% chromic acid or in an 8% nitric - Z% sulfuric acid etch.
50 ppm FC-95 sharply raises the rate of attack.

FC-95 and FC-98 are also effective in mist suppression, eliminationof gray powder, and in producing a more desirable miscroscopically pebbled
coating in chrome pickle for magnesium. This is a sodium dichromate,nitric acid solution at 70-90°F. FC-95 is suggested at the 0.02% level;
FC-98 at 0.08%.
6.

COPPER STRIKES

FC-134 and FX-161 are effective in a 3% copper sulfate, 3% sulfuric
acid, 0.5% Carbowax Z0M formulation. Used at the 0.0 1-0. 1% level, thesesurfactants allow a several-fold increase in immersion time for the samedeposition of copper. This results in a plating which is considerably more
durable.

- 3? -

3MA01201666

1042.0038

ELECTROLYTIC PROCESSES
1.

CHKOME PLATING (5, 6)

FG-95 andFG-98 possess extreme chemical resistance and surface
activity in acid media. They are used to eliminate misting of decorative
chrome plating baths, du_e to their ability to develop stable, fine foam
blankets on top of the bath.
In addition, drag out losses are reduced
considerably and hazards to operating personnel are minimized.
Decreased exhaust velocities and reductions in corrosion of exhaustsystems is also attained.

These surfactants generally leave some pin holes in hard chrome
plates but can be used to advantage in those applications where such aneffect is tenable.
NICKEL PLATING
FX-161, 20 ppm, is useful as a non-foaming surfactant in the Watts
type bright nickel plating bath.
A significant reduction in surface tensionof the bath is effected even at this low concentration.

3.

ELECTROCHEMICAL MILLING

FC-128 has been shown effective in increasing the rate of metal
removal in these applications at 10-100 ppm concentrations. Surface
tension of a 25~0 sulfuric acid drilling electrolyte for a nickel alloy was
reduced from 75 to Z5 dynes/era.

FX-161 at I0-I00 ppm increases the rate of milling by a factor of
about 2 without foaming. FC-I Z8 causes foaming at these concentrations.

- 38 -

3MA01201667

1042.0039

EVAPORATION INHIBITION

P~educing losses from evaporation is readily accomplished throughThe following illustrates the types
the use of fluorochemical surfactants.

of effects obtained in this application.
1.

1, 1, 1-Trichloroethane - Tests were conducted in open beakers,

not in a draft, at room temperature
SOLVENT I~ETENTIO~
after 114 hours

SAMPLE

1990
9Z

Control
0.01% FX-17Z
0.1% FX-17Z

2.
Methylene Chloride - Tests were conducted in wide-mouth jars atroom temperature in the draft of a laboratory hood. Approximating

commercial practice, a layer of water was floated on the top of thesolvent. The height of each phase remaining after 2 days is recorded.

Sur factant Used
Water Phase
Original thickness, mm.
P~etention, %Methylene Chloride Phase
Original thickness, mm

Retention, %FX-172None

FC-IZ8

FC-I 34

11.5
0

14.0
Zl

14.0
II

6.5
0

57.5
ZZ

75.5
98.7

76.0
98.7

75.5 .
91.4

A sample with no water layer and no surfactant evaporated to dryness
within six hours. FO-128 and FC-134were used at 100 ppminthe waterphase; FX-172 at I00 ppm in the methylene chloride phase.

3.
JP-I Aviation Kerosene - This jet fuel was evaluated at 140°F ina laboratory hood for 84’ hours.
FUEL RETENTION
after 84 hours

SAMPLEC ont r ol
100 ppm FX-172

52%
63%

Inhibition of solvent evaporation with fluorochemical surfactants ishighly specific as to the solvent type. Our laboratories will be pleased
to assist in selecting the best surfactant for a particular solvent.

- 39 -

3MA01201668

1042.0040

PICKLING O1< DESCALING OF STAINLESS STEEL

A 10% hydrochloric acid bath is effectively inhibited by 0.01%
FC-134.

Corrosion is essentially stopped 30-60 seconds after immersion.

I%ESINS AND PLASTICS

The addition of Fluorochemical Surfactants to liquid resins reduces
their surface tensions considerably. For example, the addition o£ 0.1%
FC-134 to a liquid epoxy resin, reduced the surface tension to 34 dynes/cm.
after 1 hour (from 48 dynes]cm, without surfactant). Such effects can beused to advantage to speed up the wetting of glass fibers or other fillers
for the resin, to increase the rate of release of trapped air bubbles fromthese viscous resin systems, and to improve wetting of concrete, metal orother substrates to which they may be applied.
FC- 170 in 0.1% concentration added to a phenolic resin (55% solids)
from a 50:50 cellosolve:water solution, will reduce surface .tension from46.5 dynes/cm, to 24. Z dynes/cm. Improved speed and.~th6roughness ofwetting asbestos or other fillers will result.
FC-1 Z8 and FC-170 may be used as wetting, a~gents for water on polyethylene or other plastics. Unlike conventional surface active agents,
they do not cause stress-cracking.

In many resin systems, water, oil, or ’soil resistance can be upgradedby the incorporation of small quantities of 5M ]~rand Fluorochemical
Sur factants.
SOLVENTS

FC-128 and FX-161 speed up the rate of removal of epoxy resin
based paints from magnesium and al~rninum by methylene chloride paintstrippers. Solvent evaporation maybe reduced by certain fluorochemical
surfactants. This effect is highly selective depending on the particularsolvent involved since the solubility of the surfactant in the solvent is anextremely important factor. See the Evaporation Inhibition Section.

- 40 -

3MA01201669

1042.0041

WATER TREATMENTS

1.

Open Cooling Water Systems (8)Laboratory studies indicated low corrosion rates would be obtainedon mild steel in synthetic coolir, g water if FC-95 were used in conjunction
with the noraml chromatic inhibitor. A summary of these 6-day test resultsof corrosion rate in mils per year follows:
CORROSION RATES OF MILD STEEL CORROSOMETERPROBES IN SYNTHETIC COOLING WATER
CORROSION RATE,
Mils Per YearINHIBITOR

60+

None
15 ppm Chromates
Z5 ppm Chromate
40 ppm Chromate

7.5
4.6
3.3

5 ppm FC-95 + 15 ppm Chromate*
5 ppm FC-95 +,40 ppm Chromate

3.2
0.6

I0 ppm FC-95 + 15 ppm Chromate*
I0 ppm FC-95 + 25 ppm Chromate
10 ppm FC-95 + 40 ppm Chromate

Z.9
0.4
0.4

*pH 4.0-4.5; all others pH 6.5-7.5

As a result of this laboratory work, this effect was verified in aforced draft cooling tower for 300 ton air conditioning condenser. The
cooling system operated twelve hours a day and had a cap~acity of 3000
gallons. The circulating water temperature averaged 85-F., and the heatexchanger surface temperature was about i05°F. Circulation rate was
900 gpm, and blow-down averaged 4 gpm initially. After the first 49 daysof the 115-day test, blowdownwas discontinued to increase the scaling
potential of the water.
Results were monitored with mild steel Corrosometer probes.
With no inhibitor, a corrosion rate of 73 mpy was obtained. A level of
60 ppm chromate for filming the system, followed by 15 ppm chromate
for film maintenance gave a Z. 5 mpy corrosion rate.
The addition of l0
ppm FC-95 to the 15 ppm chromate reduced the rate to 1.2 mpy in 3 weeks
and to 0.9 mpy in 7 weeks. Duplication of the synergistic effect noted in
the laboratory work was excellent.
Closed Heating System (8)Another application of fluorochemical surfactants in the water
treatment field has been in closed heating systems. Their use as acorrosion inhibitor in these systems evolved during an investigation ofa somewhat unrelated problem, that of wear on pump seal rings in closed
heating systems..

41 -3MA01201670

1042.0042

Z.

Closed Heating System (8) (continued)
The graphite seal rings were wearing to failure at a rapid rate insystems inhibited with 300 ppm chromate.
It was believed that most of
this wear was due to the evaporation of the high chrom~te water at theseal surface forming abrasive chromate crystals.
One of the systems in which a failure had taken place was charged

with the combination Z5 ppm chromate - I0 ppm FC-95. New graphite
seal rings were measured by micrometer and installed in the pumps.
Mild steel and Admiralty brass probes also were installed in the system.
Results of this evaluation are shown below:

CORROSION AND SEAL WEAI~ EVALUATION

CORI~OSION IIATE, mpy SEAL RING WEAR
" SteelAdmiralty
mils/month

PERIODINHIBITOi~

8.5 months
6 weeks
8 months

None
500 ppm Chromate
25 ppm chromate+ I0 ppm FC-95

i. 1
0.4
0. I

0.1

i. 6
28.6
0.4

It is seen that besides maintaining or reducing the low corrosion rate,
the FC-95 - low chromate combination inhibitor markedly reduced seal wear
rates. It is possible that the surfactant is also acting as a surface lubricant
on the seal rings.

4Z-

3MA01201671

1042.0043

WAXES

1.

Alkaline Systems

Self-polishing floor waxes, based on polystyrene or acrylic emulsions
are an excellent application for fluorodhemical surfactants (7).
These
products require a high gloss, excellent durability to acid or neutral media,
ease of application, stain and abrasion resistance, re-buffability, recoatability, and ready removal with alkaline cleaners.

A typical formulation follows :85 pbw - ]Emulsion polymer, 40% solids
5-10 pbw - Wax emulsion
5-10 pbw - Alkali soluble resin

Z pbw - Plasticizer
1 pbw - Fluorochemical surfactant, i% solution

The emulsion polymer is the basic vehicle and can be acrylic, styrene,or a blend of the two. The wax emulsion gives buffability to the system.
In the acrylic system, the alkali soluble resin acts as a leveling agent,
while in the polystyrene system it acts as a carrier for the polymer andpromotes ease of removal with alkaline cleaners. A plasticizer is required
for the styrene systems - not for the acrylics. FC-IZ8 or FC-134 are used
to improve leveling, gloss, wetting power, and minimize streaking. At
low concentrations (70 parts per million) no adverse effects on water
resistance are noted.

2.

"Lock and Key" Systems
The "Lock and Key" systems are those which employ resins which are

insoluble in alkaline compounds, such as soaps and detergents, and which
can be easily removed with acidic cleaners. The major advantages of thesesystems are:(i.)

Scrubability with household cleaner s without r emoving thefinish.

(Z.)

Higher gloss due to easy re-coatability, and(3.)

Easy removal.

Formulation of these products is basically the same as the alkaline
soluble systems, excpt that the resins are modified for acid solubility -alkali insolubility. Here, again, the fL, orochemical surfactant does
what normal surfactants could do in improving the compatibility and/or
solubility of the various phases in each other, but at a level which will
not cause sensitivity of the dried film to water or alkali
In applications of this type, it is recommended that both FC-IZ8 andFC-134 be evaluated and compared.

- 43 -

3MA01201672

1042.0044

TOXICITY

Toxicity classifications of 3M Brand Fluorochemical Surfactants
range from slightly toxic to moderately toxic. Listed below are LD50
values obtained by determination of acute oral dosage to adult rats and
mice.
LD50
C LASSIFIC AT IOIW
gm/IKg of Body Wgt.
SURFAG TAINT
FG -9 50.45

moderately toxic

FG-98

0.18

moderately toxic

FG -1 Z8

0.75

slightly toxic

FC-I 34

0.5

slightly toxic

FX-161

6.2

slightly toxic

FC- 170

3. Z

slightly toxic

FX-17Z

2.0

slightly toxic

Due care should be exercised in handling these materials until
further information is availabl,e on their physiological properties.

- 44 -

3MA01201673

1042.0045

BIB LIOGRAPH Y"Surface Chemistry, Theory and Applications, " J. J. Bikerman,
Second Edition, 1958, Academic Press, Inc., pp. 4-23.

"Surface Chemistry, Theory and Industrial Applications, "Lloyd I. Osipow, ACS Monograph 153, 1962, Reinhold Publishing
Corporation, pp. 18-21.

3.

Ellison, A. H., and Zisman, W.A., J. Phys. Chem., 58:260 (1954)
Guenthner, i~. A., and Vietor, M. L., I & E C Product Research andDevelopment, I: 165 (1962)
Absolute Control of Chromic Acid IV[ist; G. Hama, W. Frederick,
D. !Vlillage, and H. Brown; American Industrial Hygiene Association
Quarterly, 15: 3, September, 1954.

6.

U.S. Patents Z, 750,334 and Z,750, 337.

7.

U.S. Patent 2,937,098.
"Fluorochemical Surfactants Control Diverse Corrosion Problems,
R. D. Burke, J. B. Kittredge, J. S. Spira and i%1. L. Vietor,
presented at the 1963 Gonference of the National Association ofCorrosion Engineers, New York, N. Y., March 14, 1963.

- 45 -

3MA01201674

1042.0046

BRANCH OFFICES
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Chamblee, Georgia
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3MA01201675

1042.0047