Parts Cleaning

Pollution Prevention
Information Packet

January 1996

Prepared by
Office of Pollution Prevention
Ohio EPA
P.O. Box 1049
Columbus, OH 432 16- 1049
(614) 644-3469
I
 Parts Cleaning
Pollution Prevention Information Packet

Can you use more information about making your cleaning operations more profitable? More likely to be in
compliance, or better? More environmentallyfriendly, using pollution prevention? And, who sells the necessary
equipment and materials? Would you like to get the basics in one place? Ohio EPA's Office of Pollution
Prevention has done someof that work for you. This packet has severalof the best, most beneficial and commonly
referenced technical papers available in this area. We are pleased to provide this information to help make yourjob
easier.

Pollution preventionoffers you some ofthe best opportunities to reach each of yourobjectives above. Please use
these references as guidance, and contact theOfice of Pollution Prevention if you would likefurther information.

The information packetcontains the following articles:

Introduction
1. Kuhn, A.T. 1993. Is it Clean? Testingfor Cleunliness of Metal Surfaces. Metal Finishing 9 1(9):25-3 1.

2. Jones, W.C. 1985. Testing Surfacefor Cleanliness. Metal Finishing 83(10): 13-15.

3. Fromm, C.H., S. Budaraju, and S.A. Cordery. 1988. Minimization ofprocess Equipment Cleaning Waste.
Solvent Waste Reduction Alternatives Seminar: Speakers Notes. CERI-88-06. U.S. Environmental Protection
Agency, Centerfor Environmental Research and Information and Ofice of Solid Waste and Emergency
Response, Washington, D.C. 17pp.

Alternatives in General
4. U.S. EPA. 1994. Guide to Cleaner Technologies: Alternativesto
Chlorinated Solvents for Cleaning and Degreasing. Available Pollution prevention means
Technologiesfor Alternatives to Chlorinated Solvents for Cleaning the use of Source reduction
and Degreasing: Descriptive Aspects and Operational Aspects techniques in order to reduce
(Tables 2 and 3). EPA/625/R-93/016. U.S. Environmental risk to public health, safety,
Protection Agency, Office of Research and Development, welfare and the environment
Washington, D.C. 5pp. and, as second preference, the
use of environmentallysound
5.New Jersey Technical Assistance Program.1994. Know Your recycling to achieve these same
Cleaning Alternatives. The Catalyst 1(2):4-5. New Jersey
goals. Pollution prevention
Technical Assistance Program, Newark.
avoids cross-media transfersof
Aqueous & Semi-Aqueous Cleaning waste and/or pollutants and is
6 . Michigan Departments of Commerce and Natural Resources. 1994. multimedia in scope. It
Aqueous and Semi-Aqueous Cleaners. Fact Sheet #9409. addresses all types of waste and
Environmental Services Division, Michigan Departments of environmental releases to the
Commerce and Natural Resources, Lansing. 16pp. air, water and land.

7. Durkee 11, J. 1994. Semi-Aqueous Cleaning: Is It For You.

Products Finishing 59( 1):62-68.

8. Ohio EPA. 1995. Extending the Life of Aqueous Cleaning Solutions. Fact Sheet No. 3 1. Office of Pollution
Prevention, Ohio Environmental Protection Agency, Columbus.6pp.
Other Afiernatives
9. U.S. EPA. 1994. Guide to Cleaner Technologies: Organic Coating Removal. Available Cleaner Technologies
for Coating Removal: Descriptive Aspects and Operational Aspects (Tables I and 2). EPAl625lR-9310 15.
U.S. Environmental Protection Agency,Office of Research and Development, Washington, D.C. 6pp.

10. Konopka, J.E. 1987. Gentle Blast: Plastic Blast Media Removes Paint andsurface Soils Without Harming
Substrates. Products Finishing 5 1(1 1): 74-8 1.

1 1. U.S. DOE. 1994. Supercritical C02: An Environmentally Acceptable Alternativefor Industrial Cleaning
Applications. Industrial Innovations for Tomorrow. Office of Industrial Technologies, U.S. Department of
Energy, Washington, D.C. 2pp.

12. U.S. EPA. 1994. Guide to Cleaner Technologies: Alternativesto Chlorinated Solvents for Cleaning and
Degreasing. Available Technologies: Supercritical Fluids. EPA/625/R-93/016. Environmental Protection
Agency, Office of Research and Development, Washington, D.C. 4pp.

13. U.S. EPA. 1994. Guide to Cleaner Technologies: Alternativesto Chlorinated Solvents for Cleaning and
Degreasing. Available Technologies: Carbon Dioxide Snow. EPA/625/R-93/0 16. Environmental Protection
Agency, Office of Research and Development, Washington,D.C. 3pp.

14. 'Durkee 11, J.B. 1995. RegulationsAfecting Aqueous CleaningSystems. Products Finishing 59(8): 100-102.

A listing of potential vendorscan be found atthe end of the information packet. This list is not necessarily a
complete listing of vendors, but is being provided
to help identify andlocate vendors ofpollution prevention
equipment and supplies. Ohio EPA does not endorse any ofthese vendors, but provides this information as a
service to Ohio businesses.

The U. S. Environmental Protection Agency's Enviro$en$e is a useful tool when selecting an alternative solvent.
Enviro$en$e is host to a computerized expert system known as the Solvent Umbrella. The Solvent Umbrella
allows users to find alternative solvent information through a single, easy-to-use command structure. In particular
Enviro$en$e provides a link to the Solvents Alternatives Guide (SAGE). SAGE is an expert system that initially
evaluates the user's current operating scenario. Next SAGE identifies possible alternative solvent chemistries and
processes that best suits the defined operating and material requirements. Enviro$en$e is accessible through the
Internet at http://es.inel.gov or by modem at (703) 908-2092. SAGE is accessible within the Solvent Substitution
Data Systems section of Enviro$en$e.

Besides this information packet, the Office of Pollution Prevention (OPP) of Ohio EPA providesother types of
technical assistance. OPP provides industry specific pollution prevention from over-the-phoneconsultations to on-
site pollution prevention assessments. All services are non-regulatory and providedfree-of-charge. OPP also
coordinates voluntary pollution prevention programs suchas Green Lights and Ohio Prevention First. In
cooperation withthe Ohio Department of Development, OPPadministers a pollution prevention loan program. This
program loans funds for existing facilities to acquire or renovate machinery and equipmentfor pollution prevention
practices. For further information on any of OPP's program contact OPP at (614) 644-3469, or point your Internet
World Wide Web browser to:http://www.epa.ohio.gov/opp/oppmain.html.
 1s It Clean? Testing for Cleanliness of Metal
Surfaces
by Anselm T. Kuhn,
Finishing Publications Ltd., Stevenage, Hertfordshire,England
CLEANLINESS:
UNGLAMOROUS BUT VITAL!
R
egular readersof Metal Finish-
ing would probablyfind
it
‘mpossibletolocate a single
issue of thejournal in which, one way
or another, the cleaningof metals prior
to their subsequent surface treatment is
not mentioned somewhere. Expert
after expert delivers the same simple
message-pr cleaning isthemost
commonsingle cause of defectinci-
dence o r coating failures. Among the
mostcommon failures from poor
cleaning, we can mention poor adhe-
sion of coatings, poor corrosion resis-
tance, blistering and pitting, failure to
pass specificatiodstandards testsand
stained and/or irregular coatings.
To make matters worse,veryfew
metal-finishing processestoday are
based on a single coating.Duplex
metal coatings, metal plus conversion
coatings or metal plus organic coatings’
arecommonlyfoundcombinations.
When these fail, it is mostly the outer
layerthatmanifeststhefailure-but
what is the real cause? AI1 too often,it
goesrightback to the lowest of the
coatings-and the cause is incomect
cleaning.Troubleshootingsuchsitua-
tions is an exercise mostfinishers
(except those who fancy themselves
“private eyes”) can do without.
All of the foregoing is as true today
as it has been since finishing began;
but thanks to new environmentallegis-
lation, nearly all metal finishers in the
United States and Europe
have
changed (or are about to change) their
cleaningtechnologies. This might
mean new equipment using traditional
organic chlorinated solvents, such that
theirescape into the atmosphere is
controlled. It might mean new organic
solvents, such as terpenes, or aqueous
semiaqueous
or cleaning
systems.
Metal finishinghas been getting mixed
messages on this front. Some finishers
who haveconverted to aqueous or
semiaqueous systems haveexpressed
METAL FINISHING SEPTEMBER 1993 0 Copyright Elsevier
themselves as totally satisfied. Others
grudgingly accept that the new meth-
ods will do the job but still consider
thatsolventcleaning gave a cleaner
surfaceorwasmore“forgiving”to
operate as a process. We haveeven
heard of a handful of plantsthat,
havingmadetheswitch,reverted to
solvent cleaning after what they saw as
a disastrousexperiment.Whichever
thecase, nowmorethanever,metal
finishers should be on their toesand
asking themselves, “Is it clean?’
What Do We Mean by “Clean”?
The answer to this question depends
on
the
metal-finishing
process se-
quence being used. The most common
form of surface contamination is oils or
greases that originate from mechanical
processing, such as rolling, or are
deliberatelyapplied as a temporary
protective coating for storage or ship
ping. Mold-release agents are another
source of such films and, if based on
silicones, are arguably the most diffi-
cult
to
remove of all
such
films
encountered by the finisher. Films of
organic coatings such as these are bad
news for nearly allmetal-finishing
processes. The onlyexception that
comes to- mjndinvolvessolutions
confaining strong oxidizing agents
such as chromic acid, so chromium
plating (but not the nickel deposition
that usually precedes it) and chromic
acid anodizing are two treatment proc-
essesthat can probablytolerate the
presence of organic film contaminants,
although, even here,no one is suggest-
ing that this should be put to the test.
Other forms of surface contamina-
tion
can
broadly be classified as
“chemical” (e.g, oxides) or “particu-
late” (dust). Ofthese, one canmake
thefollowingcomments.Oxidesand
hydroxides
will be removedby
cathodic cleaning, by picklingorin-
deedby the cathodicnature of elec-
trodepositionprocesses
themselves.
Particulatescangive rise to plating
Science Publishing co., Inc.
KuhR AT. 1993. is I ( Clean7
Testing for Cleanhners ofMetai
.%?$aces. Metal Finishing
91(9):25-31. Reprinted with
permission &om Elsevier Science
IIlC.
problems, causing rough deposits and
sometimespits;however,unlikeor-
ganic films, they can readily be Seen
either withthenakedeye or with a
low-powermagnifyingglass.Ascer-
tainingtheirpresence on thesurface
therefore presents no great challenge.
In short, in mainstream metal finishing,
the presence of organic films is both
inimicaltosuccessfulfinishingand
difficult to detect.
Intheprintedcircuitboard (PCB)
and related industries, organic contam-
ination as describedabove is equally
undesirable,insofar as electroplating
andelectrolessdeposition are key
operations; however, a totally different
formof surface contaminationis no
less critical, namely that due to ioor-
ganic salts, usually as a result of
incomplete rinsing from preceding
platingoperations.Suchresidues,on
the surface of a PCB, permitthe
passage of stray (“parasitic”) currents
that can cause premature failure as a
result of corrosion(these salts are
frequently hygroscopic). This process
is sometimes known as “tracking.”
To detectsuchcontaminants,the
PCB industry has evolved standard test
patternsformeasurement of surface
insulation resistance. In addition, con-
ductivity measurements of rinse water
provide a means by which the danger
oflow surfaceinsulationresistance
values can be signaled.The.Institute
for Interconnecting and Packaging
ElectronicCircuitscoordinatessuch
standards for the industry. Mainstream
finishers in theUnitedStates,the
United Kingdom and most other coun-
hies havenoAmericanSocietyfor
Testing and Materials specification or
similar standard to guide them.
How Clean Should a Surface Be?
There have been various attemptsto
provide a quantitative basis for meas-
uring
surface
cleanliness;
however,
anysuchunitsmusttosomeextent
depend on the natureof the soil and the
25
 method used for its measurement (e.g.,
chemical or physical). Thereis thus no
simple answer to the question of how
clean a surfaceshouldbe,beyond
suggestingthat if a suitable testhas
been found, the results of that test can
bematchedtotheperformanceof
whateversurfacetreatmentissubse-
quently applied. Without doubt, some
processes are far more sensitive to the
presence of soiled surfaces than others.
In some cases,the
actual
surface
treatment process incorporates itsown
cleaning action.
Vacuum-basedmethods are also a
possibility for cleaning surfaces. Even
in a moderate vacuum, lowering total
pressurewill
increasethe
rate of
evaporation ofan organicfromthe
surface, although this may still take
many hoursto volatilize completely.In
electron or ion beam or plasma meth-
ods, the surfacecan be bombarded with
ionssuch as argonthat are highly
effective in providing a new and
therefore clean surface.
As a generalization, it is probably
true that water-based coating processes
are more sensitive to even monolayers
of organic surface contamination than
solvent-based paint processes. In the
latter case, because there will almost
certainly be somemutualsolubility
between the organic contaminant and
the solvent in the paint, the “ M e r ”
effect that operates in the caseof
aqueous processes willlargely disap
pear.
METHODS FOR MEASURING
SURFACE CLEANLINESS
The importance of beingableto
assess surface cleanliness wasrecog-
.. .
nizedearly inthe 19th century. In
surveying the literatureon the subject,
’ there is no doubt that a high point was
the American Electroplaters and Sur-
faceFinishersSociety(AESF)-spon-
soredresearchproject in theearly
195Os, headed by H.B. Linford. This
project, a modelofits kind,started
withan
exhaustivereview of the
literature, went on to make a quantita-
tivecomparison ofthevarious tests
and concludedby suggesting modifica- OVERVIEW OF SIMPLE
tions to some of the older methods. TheMETHODS
results werepublished in successive
issues of PZ~ting”’~andwere also
issued by the AESF in booklet form. be implementedwithout any special-
The first industrially significant test
for surface cleanliness goes back to the semiquantitative, at worst subjective.
26
AmericanCivilWar,whenphotogra-
phersrecognizedtheimportance of
having clean glass plates before appli-
cation of the photographic emulsion to
the plate surface.12 Since then, a num-
ber of methods have been developed
for measuring surface cleanliness.
0 Visual(optical,microscopic)
Waterbreak
0 Spray/atomizer
0 Fluorescence
0 Contactangle
Radiotracer
0 Stimulatedelectronemission
0 Attenuatedtotalreflection spec-
troscopy
0 Combustion and
carbon dioxide
analysis
0 Surfaceconductivity
0 Scanningelectronmicroscopy
0 Augerspectroscopy, ESCA
0 Ellipsometry
Analysisofwashings
0 Copperdisplacement
0 Dyemethods
0 Other
These methods can be characterized
in two different ways. First, there are
complexmethodsthat can onlybe
carried out in well-equipped laborato-
ries. These contrast with the simpler
methods that were devised to be used
either on the production line or in a
verymodestlyequippedproduction
laboratory. Second, there are methods
that indicate only the degree of cleanli-
ness, without offering any insight into
the
nature
of
the
contaminant,in
contrastwithothertechniquesthat
actually provide a degree of “chemi-
cal”infqrmation. Examples are (in the
first category) techniques that measure
wetting or contactangle and(in the
secondcategory)attenuated total re-
flection spectroscopy.
Although the purpose of this report
is to provide the most extensive over-
view possible ofsuchmethods, the
simpler methods are emphasized. For
those with the means and resources to
pursue the more complex techniques,
the relevant literature is cited.
The following methods can usually
ized
equipment.
They are at best
METAL FINISHING
Visual and Optical Inspection
Visual inspection of a bright me
surface by eye reveals only the gross’
soils. Neither passive oxide films I
thtn layers of grease are thus be to sel
Ellis14mentionssuchinspection
well as that enhanced by the use o
hand-held magnifier. Although the I
ter enables finer particulate soils to
seen, the invisibilityof oxide or gre;
layersremains.Evenifanopti
microscope is used, this isstill tr
and although the latterallows partic
down to the limit of optical resoluti
(governed by the wavelength of lig
tobe seen,caremustbetaken d
airbornedustparticles do notfals
theresults by settlingon the t
surface during the
examination
whilethesampleis in transit to I
microscope.
Another visual method is towipe i
surface with a paper tissueor a piece
white cloth, suchas cheesecloth, w h
can then be inspected by eye or wid
magnifying glass.A white cottonglc
can also be used.Thisapproach 1
been described by Linford and Saul
stre.’ In cases where the sample is I
bright and smooth, visual examinati
is of little use, whereas the wipi
method may provide some insights.
Even the simple approach based
wipingcanbemadequantitative,
suggestedbyBrandon.15 A pressu
sensitive tape is used to pick
particulate soil and this is then vie%
in a densitometer,whichrecords 1
change in optical density resulti
from pickupof the soil.
Wetting Behavior
A cleanmetal surface is “hyd
philic” andwillthus be fully “w
ted” by water. The presence of
willprevent this, and,rather tk
spreading as a uniform thin film, 1
water or moisturewillbreak up il
discrete droplets. Passive oxide lay1
behave no differently from pure me
in this respect,andwaterwetting
thus not a test for the presence of sc
layers. From t h i s principle, a numl
of tests have been devised.
Breath Test
Simply by breathing onto a surfr
and observing the result,
a jud-pent
cleanlinesscanbeformed. A cle
surface produces a uniform cloudi~
A greasy one will show droplets.
0 SEPTEMBER 1ti
 Water-Break Test
Water is applied to the metal sur-
face, usually inclined at approximately
450 to the vertical. The formation of
discrete droplets suggests the presence
of hydrophobic impurities on the sur-
face. usually of long-chain hydrocar-
bons. Lutterl6 points out that another
cause maybe the use of hard water.
Calcium ions can react with long-chain
fatty acids to form hydrophobic metal
soaps. If this is suspected, the test
should be repeatedwithdeionized
water. Lutter makes the further point
that, in plants fitted withrecycled
water from an ion-exchange unit,there
isthedanger that althoughcalcium
ions are removed, the concentrations of
nonionic surfactants will buildup, and
these can interfere with the test.
.... Cohen and HookI7 make the point
.
that this test will not detect contamina-
tion by soaps or surfactants, nor will it
detect water-wettable particles,such as
rust, oxides or other finely divided
metals. In the same way, the presence
of surfactants in the water used for this
test will interfere with the results. In
some cases,theuse of wateris undesir-
able because it can cause rapidrusting.
Cohen and Hook also mentionthat the
thinner the waterfilm used in this test,
themore sensitive it is. Still other
weaknesses in thistest are due to
“bridging”of a small ContaminaH
area by a film of water.
In anotherversion,describedby
Linford and Saubestre, panels are rap-,
idly removed from the test bath, and ’
the number of secondsfor water break
to occur are noted.Panels are with-
drawn vertically and shouldbe so held
above the solution. Alternatively,after
withdrawal,they can be inclinedat
45’. withwaterfrom a wash bottle
beingapplied,thusflooding the sur-
face for approximately 20 sec.Linford
and Saubestre7 suggest that the latter
method has a slight drawback because
it allows oil to migratedownward
during the test procedure.
Spray Pattern or Mist Test
Thistest,althoughsimilartothe
water-break test, is less sensitive tothe
presenceof soaps or surfactants and
thus forms a better basis for a simple,
routine works test. The wettedmetal
surface is sprayed froma distance of 60
cm with distilled water from a spray
gun operatedat0.6-1.0-kg/cm2 air
pressure for 30-50 sec. The resulting
METAL FINISHING * SEPTEMBER 1993
patterns are observed. Two variations
are described by Lutter.16 In the first,
which increases the sensitivity of this
test, the metal is previously etched in
1% hydrochloric acid. Inthe second,
the spray water is dyed with approxi-
mately 0.1% of a bluedyestuff.’*
CohenandHook17describehow the
methodcan be madequantitativeby
placing a sprayed panel inside a view-
ing box with a grid of IO0 squares and
tracing the pattern with a pencil. The
number of squares appearing cleanare
counted, andthis procedure is averaged
over five panels. The result, expressed
as a number (out of loo), was named
the “cleanlinessindex” by Linford
and Saubestre? An alternative proce-
dure, described by Linford and Saube-
stre, is to spray the panel aftercanying
out a water-breaktestforapproxi-
mately 15 sec. Because the panels hang
vertically, evaporation to dryness be-
gins at the top of the panel and works
its way downward until only drops at
thebottomremain. The thickness of
the resident water film is thus related to
its position on the panel, and the spray
pattern test is more sensitive near the
top ofthe panel (where the film is thin).
Even the slightest trace of oil droplets
nearthetopof the panelcancause
quite widespread areas being formed in
thespray pattern, whereas near the
bottom, the water droplets only form
directlyabovethe oil droplet. This
makes the time
factor
critical. In
laboratory conditions, clean areas will
typicallyremainwetted for upto a
minute,afterwhich dry patcheswill
appear, initially at the top edge of the
panel;however, if spraying is com-
menced teo y o n (less than 45 sec after
-age), some areas of potential
waterbreak may still be wetted be-
cause there is still a fairly thick water
film on the surface.
Atomizer .Test
This variant of the spray pattern test
wasdevised by LinfordandSaube-
stre? The test is applied toa dry, not a
wetted, surface. The resulting wetting
action requiresa higher surface energy
than for the already wetted surface of
the spray test. In consequence, thistest
is moresensitive to the presenceof
small amounts of grease, etc. Cleanli-
ness can be assessed in terms of the
area of wettedsurfaceand also by
estimation of thecontactangleof
residual nonwetted water droplets?
Mercury Droplet Wetting Test
If a droplet of mercury is placed on
a trulycleanmetalsurface, it will
spread. The presenceof grease will
cause it to retain a roughly s p h a i d
shape. The Same is true (and hert the
mercury behaves unlike warn) if oxide
films are present at the surfact.
Talc Test
Thesmoothsurface to be tested
(metallic or nonmetallic) is low&
vertically into a container of water, the
Surface of which has beendust&
lightly with talc. The interaction of the
talc particles with the smoothSUrfaeis
observed.
This
method has de-
scribed by Donelson and Neish.19
Another use of talc or lycopodium
powder is described by Lutter.16This is
not used directly as a cleanliness test
but to detect the presence oily of layers
on the surface of a cleaning bath.It will
be evident that where such layers are
present,however much a metalis
cleaned by immersion in solution, on
beingraisedfromthecleaningsolu-
tion, it willpassthroughsuchoily
films andbecontaminatedbythem.
According to Lutter, when paraffins or
other nonpolar hydrocarbons are pre-
sent on the surface. they form spherical
or lens-shapedglobules. In thepres-
enceofpolarsubstances,such as
drawinglubricants,thehydrophobic
dust particles are displaced.
Copper Displacement Test
If a metal such as steel is i m m d . ,
in an aqueous solution
of
copper
sulfate, a so-called “displacement re-
action”willtake place-a pair of
coupledelectrochemicalreactions in
which the less noble metal(the steel) is
anodically dissolved, tobe replaced by
the more noble metal(copper) deposit-
ing fIom solution. The old school trick
of immersing a coppercoin in a
solution of silver nitrate to produce a
silver coating is anotherexample. If,
however, the metal surface is obscured
by a layer of grease, this exchange
reaction will beimpeded or maynot
take placeat all. Linford and Saubestra
recommend the
following
solution
composition: 63 g/L. copper sulfate
(pentahydrate) and 17 g/L sulfuric
acid.
The panels are dipped rapidly into
solution,heldmotionless for 10 sec
andthenremovedrapidlyand trans-
27
 ferred to a beaker of distilled water in
whichthey are agitatedfor 15 sec.
They are then hung vertically, washed
for 20 sec withwaterfrom a wash
bottleandallowedto dry, preferably
using radiant heat from a bright light
source, for example. Ether extraction is
used to removeanyremainingoil
patches, and the panels are then exam-
ined.
Potassium FerricyanideTest
(Ferrous Surfaces Only)
Rag-bondpaper is cutintostrips
approximately 6 x 12 cm. It is coated
on one side with a solution of 50 g/L
crystalline whitegelatinand 50 g/L
sodiumchloride
(chemicallypure
grade will do). The strips are laid flat
on a sheet of glass, and a glass rod,
dipped in solution, is rolled from one
side to theother. This processis
. repeated four times. The paper is then
allowed to dry and can be stored ready
for use.Before testing, thepaper is
soakedforuptohalfanhourinthe
following solution: 50 g/L sodium
chloride, 10 g/L potassiumferricya-
nide and 1 g/L. hydrochloric acid.
Linford and Saubestre’ make the point
that it is wise to include acidinthe
aboveformulationbecause,should it
be omitted, the bluecolor formed tends
to be streaky andlight,makin the
d
identification ofoily patches di cult.
The test piece (a metal panel)is laid
flaton a pieceofglass,andthe
impregnatedpaper is appliedto its
surface, with the gelatincoated side in
contactwith the metal. A glass rod
covered with an 8 c m length of rubber
tubing is rubbed briskly over the metal
surface for approximately 15 sec. Ad-
ditional test solutionis poured over the
paperuntil it is completelyremois-
’ tened. After 3 min of contact, the paper
is removed and allowed to dry.Clean
areas will be relatively dark blue on the
test paper, whereas oilcontaminated
regionswill appear as colorlessor
yellowish zones. No notice should be
takenoftheodd streakiness in blue
zones,whichmaybedue to poor
surface contact, bad drying or oxida-
tion. This is especially truewithre-
spect to the areas close to the edges. If
the time of contactis too long, the blue
color will partly disappear.
Linfordand Saubestre suggestan
alternative procedure(generallyless
satisfactory),and this is to dip the
28
panel,after
testing,
into 1 vol 9% Animal fats did not producesimil
hydrochloricacidandstudytheblue solids.
pattern. Pollack and Westphalm quote, Lutter16makesthepoint that b
as a source of information, an article by causesuch a widerange of organ
Macnaughton.21 compounds fluoresce, the presence 1
dust particles can interfere. Likewis
Fluorescence Test many surfactantswillfluoresce, ar
Some mineral oils and greases will these will give false indications evt
fluoresce in UV light, andthis has been where they are present as fully wate
used as a quantitative means of esti- soluble species. A further criticism t
matingtheamountspresent.uFor the test is that hydroarbon-solub
those greases (mainly animal or vege- dyestuffs can be water solubilized t
table) that do not themselves fluoresce, synergistic effects (i-e.,made hydrt
use of a hydrocarbon-soluble indicator philic). In consequence, the degreasir
dyestuff may be made. ljpically, UV solutionand,equally,the
adhere
radiation of approximately 365 nm is water layer ‘on the test sample beir
used. In its crudest form, a subjective withdrawn from it,may contain su(
assessmentcanbemadeusingcom- water-solubilized dyestuffs, which,b
merciallyavailable UV lightsources. cause they fluoresce, will again inte
To place the teston a quantitative fere with the test.24
basis, the results are photographically
recorded, using a W filter. The sensi- Dye Test
tivityofthemethodis linked tothe This test,againdescribed byLu
lengthofthe photographicexposure, ter,I6 seems little known outside Ge
which can range from 1 min to 1 hr. many. A sample of the cleaning sol;
Such time
extension increases
the tion is placed in a beaker and raised
sensitivity by approximately 15 times its prescribed operating temperature.
and allows residuesof some 0.12 glm2 sample of metal for degreasingis tht
to be measured.U Since the time that introduced. As a result, the heavy sc
this sensitivity was quoted, there have components (some inorganic, son
been advances in both film sensitivity organic) settle atthebottom of tl
and fluorescence activity of dyes. One beaker,whereaslighteroily comp
wouldthereforeexpectevenlower nentsfloat on thesurface. An oi
amounts of soil to be detected. soluble,water-insolubledye is tht
Linford and S a ~ b e s t r e ~used
- ~ both added, such as Sudan blue. This colo
thehydrophobicphase as well
mineral and lardoils to test degreasing
procedures, and both of these are only surface films of metal soaps or mom
faintly fluorescent in W. They there- molecular layers, rendering them vis
fore usedthe dye fluorescent green ble. The bath is then stirred, using
Although this is described as magnetic stirrer. To facilitate cornpa
being “oil soluble,” theyfound it son, a constant stirring speed should 1
impossible todissolve sufficiently high set. By study of the system, especial
‘axcentrations andthereforeresorted from the size ofthedroplets of tl
to an indirect technique.Approxi- blue-dyed oily phase, the surface e
mately 1.7 g of dye was dissolved in 50 ergy and thus the cleaning efficacy
ml of solvent (Linford and Saubestre the solution canbe judged. The small
used benzene,whichwouldalmost the droplet size, the better it is. Aft
certainly be prohibited today). This stirring is switched off,the time fortl
solution was then heated over a water emulsion to re-formisnoted. Bad
bathuntil its volumewasreduced to with strong cleaning effect can mai
approximately 8 ml. A refluxing action tain the oil droplets in suspension f
downthe containerwallsprevented longer or even maintain the emulsific
crystallization of the dye.This concen- state, as shown by cloudiness of ti
trated solution was clear, dark red and solution.Depending on the type
free-flowing.Whileit was stillhot, cleaning solution used, emulsions c;
some 4.0 ml of oil was added to the be stable for hours, even days, befo
beaker, and this solution was used for breakingup to give a discreteoi
testing. In the case of mineral oil, some phase.
precipitationwasoccasionallyseen Highcapacity cleaningbaths a
after a few days, andthis was removed characterized by a transparent a
by decantation or similar methods. stable blue-colored colloidal solutio
METAL FINISHING SEPTEMBER 19!
I1 thepresence ofwhich GUI beverified
1 by a q n d @ l effect. A furtherrefine-
mentof this test is as follOWS. A
sample of the workbeingcleaned is
withdrawn from the solution.The dyed
liquid droplets should all roll off the
surface; residual oil droplets can be
w i l y detectedthanks to theircolor.
m e volume of
cleaning
solution
dragged out in this way can be easily
determined by colorimetry.
Yet another variant of this dye test
can
be canied out by dyeingthe
cleaning solution yellow, usinga color
that is totallyinsoluble in theoily
phase.Magneticstirring is applied,
and,in the presence of thefinely
divided blue-colored droplets, a com-
plementary greencolor is seen in
solution, at times only transiently. As
soon as thestirringisstopped, this
vanishes.Cleaningbathsnotsuitable
for practical use are thosein which the
blue oily phase rapidly separates from
the yellow aqueous phase, rising to the
surface.
Emulsion-typebathstested in this
way give a milkycloudinesswith a
greencolored emulsion; highcapacity
baths, in contrast, give a totally trans-
parent green solution that is stable for
extended periods of. time. Only when
such baths have reached maximum oil
uptake capacity does a discrete blue-
tinted upper layer form onthe surface!
Highcapacity cleaningbathsthat
contain emulsifying agents,solution
promotexs and hydrotropic substances
must first be tested to
determine
whetherthey are capableofsoiubil-
izing dyestuffs thatare normally insol-
uble in water.
LutterI6suggests that thedyestuff
testsdescribedabove are closeto
actual conditions, andinadditionre-
quire little time or materials to cany
out.They provide insightsintothe
behavior of cleaning baths and also of
specificlubricants or pastes used in
processing.
Clock Reaction for Copperand
Its Alloys
Granata et al.= described a simple
method, albeit one that is only useful
for copper and its alloys. This is based
on the so-called“clockreaction.”
Such reactions, well known to chem-
ists, are homogeneoussolutionreac-
tionsexhibiting a measurableinduc-
tionperiod.Strictlyspeaking,such
METAL FINISHING 0 SEPTEMBER 1993
reactions might better be described as
“alarm clock”reactionsbecause, to
the outside observer, nothing appears
to happen until the “alarm goes off,”
whenthereis,forexample, a color
change. In this case, a solution is made
upwith 0.025h4 sodiumpolysulfide.
This is formed by dilution of a 2.66M
stock solution. The copper sample is
placed in a Petri dish, and the cleanli-
ness is related to the time taken for the
sample to turn black; the cleaner the
sample, the shorter the time. Granata
al.= quote times of 16 sec for freshly
abraded copper, increasing to 40 sec
after such samples have been exposed
to the atmosphere for four days. For-
mation of oxides on the surface (e.g. by
heating in air at100’ C -for 6 hr or
immersion fora day in sodium hydrox-
ide) increases the times to blackening
to 75 and 585 sec, respectively. As an
alternative to color change, Granata et
al.
describe how a potentiometric
measurement may be carried out using
a saturatedcalomelreferenceelec-
trode.
Spreading Wetting Test
Jonesx rightly describes the water-
break test as a “go, no-go” procedure
and offers an alternative suggestion. A
series of solutions are made up, rang-
ing from 80% ethanol and 20% deion-
ized wat& to one with 1% ethanol and
99% water. These solutions exhibit a
range of surfacetension fiom 24.5
(correctedforvariations in specific
gravity) to 66 dynelcm.Above this,
solutions of potassiumcarbonate are
used to produce (800 g/L) a solution
with 101 dyndcm. By application of a
drop . ~ each’hlution
f and examination
to see whetherit fQrms a bead or a
wettingfilm,surfaces can be “cali-
brated” withregardtotheirsurface
energies.
Anotherdescriptionofthesame
approach is that by Renaudn who uses
a range of sixliquids of varying surface sensitivity -was atomizer> fluorescent
tension. A known, smallvolumeof
each liquid is dispensed (5 pl) fiom a
microsyringe, and the degree of spread sulfatedip.LinfordandSaubestre’s
is observed. Renaud rightly makes the
point that the results of thistype of test duce or even summarize here,
willdependonwhetherthere is any
physical or chemical reaction between
the test liquid and the film (if any) on second classification. in terms of the
the surface.A further expositionof the
method has been given by Cohen and
Hook,I7andBystryandPennahave
also described the use of the method.
Other SimpleMethods
Pollack and Westpha120 list most of
the above methods and others as well.
These include the following:
1. Gravimebic test-one of the least
sensitive.
2. Mean test (Elms mod$cation).
Single dropsof an aqueous solution
containing 32 mvL of 30% hydro-
et gen peroxide are applied to a sur-
face. and the time taken for corro-
sion to appearis measured. The test
is described as “not very satisfac-
tory.”
3. Simple contact angle test.
4. Oil spot test. A droplet of degreasing
solvent is applied to the so-called
clean surface and then evaporated.
Formation of a ring suggeststhe
presence of oil.
5. Rock Zsland drop resr. Distilled
waterdroplets are allowed to fall
from a specified height onto the test
surface. Themethod is saidto
distinguish between a clean surface
andonesoiledwith a 0.01% oil
solution.
6. Ring test. A drop of wateris formed
on the ringof a surfacetension
tester, and this ring is then lowered
to contactthe test surface. The
process is repeated,and the number
of such contacts required to transfer
all of the water is noted.
7. Kerosene viewing of water break A
wetted panel is dipped into a beaker
ofkerosene lit from below. Near
water breaks are displaced byk ere
sene, givinga sensitivity better than
the usual water break. The sensitiv-
ity is said to be equal to or better
than the atomizer test.
Of the simple methods that Lidord
andSaubestretestedandcompared,
theyconcluded that theranking of
dye > spraypattern(waterbreak) >
potassiumferricyanide dip > copper
work, which is too extensive to repro-
proeded
comparative data notonly for the
various methods cited above but, in a
type of grease used to contaminate the
surfaceof the metal(e.g..animal or
mineral in origin).
29
 Table 1. Sensithrity of 'Cest Methods
Method Minimum Detedable Residue (NJ Relafive Sensit@
F)uorescence 0225 1 data,includingreproducibility,
Water break 0.022 10
Radiotracer 0.002 110
MORE COMPLEX METHODS moethane.Solvent carriers werecy-
clopentane,straightforwardfreons or
Included here are techniques that do freons with 10% chloroform. The es-
call for some instrumentation, although sence of the method is that, by interac-
they require no very expensive equip- tions and mutual solubility, the pres-
ment. ence of grease onthesurfacecan
inhibit
the
rate of evaporation. A
Radiotracer Method method was described at length by
Radiolabeling was a technique very AndradSO andearlier by Hamilton.31
widelystudiedandfavoredfromthe
1950sonward,whenradioactive iso- Measurement of Contact
topes first became available. Thereare (Surface) Potential Difference
probably hundredsof
publications
G ~ t t e n p l a ndescribes
~~ thesurface
(see, e.g.,Chapter21inref.29)in
potential difference method, which,
which the adsorption of organic spe-
unfortunately, once again usesa radio-
cies on a metalsurfacehasbeen
active source.In this case, the radioac-
studied. If the first such studies were tivity is used to initiate ionization. The
made in the United Statesin the 195Os, probe is placed some 1-10 mm above
the great bulkofsubsequentwork the test surface in air, and the potential
emanatesfromtheEasternEuropean difference is electrometricallymeas-
counmes, andalthoughthemethod uredusing a high-impedanceinstru-
appears to have fallen out of favor in ment. The basis for the method is the
theWest, it continues to be used in effect that surface films have on the
Eastern Europe. The increasing availa- electronicworkfunctionof a metal
bility of radioisotopes explains therise (energy required to withdraw an elec-
in popularity of
the
method.The tron). In his report,which also cites use
subsequenttightening of IegisFtion of the method to characterize alumi-
and regulations governing the use of num after conversion coating, Gutten-
radioisotopes in laboratoriesandin plan compares its sensitivity with the
industry explains why the method has water-break test, findingit easily capa-
largelyfallenfromfavor.Indeed, it ble of detecting films thatwerenot
wouldnot be far fromthetruth to shownby the water-breaktest. The
suggest that for these reasons the report describes plans to develop a
method is nowonlyofinterest for commercially available instrument, but
historical reasons andfor very special- it issot known whether this was ever
ized research. Asa method for routine -'-produces.
industrial use it is fair to state that the Anothervariantof this method-
proceduralrequirementsinvolved in electrostatic charge decay-measures
' theuse
of radioisotopesmake the this quantity and also contact potential
method more trouble than it is worth. difference. It was developed for useon
In this spirit, it is worth reproducing the space shuttle to check the cleanli-
the data shown in Table ness of the aluminum surface on the
Radiotracermethods had a brief fuel tanks and has been described by
revival in popularity in the formof the Cibula et al.33
evaporative rate analysis method used
to characterize the cleanliness of razor Combustion Methods
blade edges. The essence of the method By introductionof a sample of metal
was to determine the rate at which a to a furnaceandpassage ofoxygen
testliquidcontaining a radiotracer over the surface, oily matter is oxidized
elementevaporatedfromthemetal to carbon dioxide and water. The
surface. As littie as 0.02 pg/cm2 of oil former speciesis determined by one of
could readily be detected in this way. a numberof analytical methods. To
Typicalradiotracersweren-tridecane ensure complete combustion to carbon
(with carbon-14) or - 1,1,2,Z-tetrabro- dioxideratherthan the monoxide, a
30 METAL FINISHING
catalytic stage is included (e.g., usi;
silver wool and barium chromate).
description of the method with typic
w
published by Kresse et al." The tec
nique is notoverlysensitive; S-
mg/m2 was used in this partied
work. Oxidation times are typically
min and oxidationtemperatures a
proximately 600°C. The criticism h
also been made that soils not contai
ingcarbonpassundetected by tl
method.
C ~ h e ndescribes
~~ a variant of t
method used by the Ford Motor Co.
follows. A fiberglass clothsaturat
with 50% hydrochloric acid is used
mop a 4-in. x 12-in. steel panel. Af
appropriate drying, the carbon contc
is determined by combustion in ox
genat 400 and 6oo°C, thecarb
dioxide being determinedin one oft
usual analytical procedures.
Contact Angle Measurements
Relatedtothespreading wetti
tests above, but more sophisticated
its approach, is the actual measuremf
of the contact angle of a sessile dn
which has been mentioned by seve
authors, including C ~ h e and
n ~ Rice
~
Washing Tests
A family of tests have been dev
oped, mainly by the electronics indl
try, in which the surface to be test&
washed with an aqueous or nonaql
ous solvent. The washings are tk
subjectedto
analysis. A trench.
criticismof this approachis that
detects only soil that has been
moved,not that remaining on
surface. In a sense, it is precisely '
latter rather than the former that is
greatestconcern. A fulltreatment
this class of test is given by Ellis.14
Analysis of Washings
Thesimplestmethodfor washil
analysis is conductimemc, and this,
Ellis describes, has formed thebasis
several commercial instruments; hc
ever, it should be clear that the PI
ence of ionic species (acids, alkalis:
salts, mainlyinorganic)isof gre;
concern to theelectronics industry tl
to themajorityofsurface treatm
processes.That said, suchconta
nants can interfere with other surf
treatment processes, for exam}
phosphating.
0 SEPTEMBER l !
 I r

I
OTHER METHODS that previously relied on superimposi- New Yo&, 1967;McBain, P. and T.
tion of grids to derive a quantitative Hutchinson, Solubilism’on and Re-
Space do& notallowmorethan a result. And, most certainly, suchis the lared Properties, p. 215,Academic
I

brief mention of other methods. Per- diversity of methods available that no Press.New York, 1955; R. Meliand,

1 hapsthe
mostuseful
for
practical
purposesistheopticallystimulated
electronemissionmethodinwhich
metal finisher should be able to offer
anyexcusesforprocessingpoorly
cleaned work.
25.
Tmilber. 40:787;1959; K. Dereser,
Angmandte Chemie. 63:327; 1951
Granata, RD. et ai., Metal Fin-
ishg,82(4):69-70; 1984
light in thevisible or W region Jones,
26.
WC., Metal
Finishing,
irradiates the surface, and the current References 83(10):13-16;1985
resulting from emission of the stimu- 1.
Linford, H.B.
and
E.B.
Saubestre, 27.
Renaud, J.-P., Oberfleche Surfme.
lated electrons is recorded. The method Plating, 37( 12): 1265-1 269; 1950 24(1):7-13; 1983
has been described by Chawla3’ and is 2.
Linford, H.B.
andE.B.
Saubestre, 28.Bystry,F.A.andL.S.Penn, Surface
of
.~-.
soecial interest because is
‘‘modem’’ instrumental method
it the only
not 3.
Plating, 38(1):60-65; 1951
Linford,H.B.and
E.B.
Saubestre,
and Interface Analysis, 5(3):98; 1983
29.Kuhn,A.T. (Ed.), Experimental Tech-
involving major financial investment. Plating, 38(2):158-166; 1951 niques in Electrochemistry. Corrosion
The use of attenuated total reflection in 4. Linford, H.B.
and
E.B.
Saubestre, and
Metal
Finishing, Wiley,
New
the infrared region can lead to identifi- Plating, 38(4):367-375; 1951 York, 1989
5. Linford, H.B.
and
E.B.
Saubestre, 30.Andrade, M., Plating and Surface
1 cation of the actual contaminants. The Plating, 38(7):713-717; 1951
surface insulation resistance method is Finishing,73(11):64-67; 1986
6.
Linford,H.B.andE.B.
Saubestre, 31.Hamilton,C.B., Plating, 62581-586;
bestcarriedoutusing a standardized Plating, 38(8):847-855; 1951 1975
“ m m ” pattern of electricallycon- 7.
Linford,H.B.andE.B.
Saubestre, 32. Guttenplan, J.D., Plating and Surface
ductingtracks on an insulating Sub- Plating,38(11):1157-1161; 1951 Finishing,65(6):54-58; 1978
strate.This is formed by thenormal 8.
Linford, H.B.
andE.B.
Saubestre, 33.Cibula, A. etal., Proceedings of the
methods used in fabrication of PCBs. Plating, 38(12):1263-1266; 1951 ASTM Symposium on Testing Metallic
Then, too, there are the methods using 9.
Linford, H.B.
andE.B.
Saubestre, and Inorganic Coatings, April, 1986
scanning electronmicroscopy (ena- Plating, 39(1):55-63; 1952 34. Kresse, J. etal., Metalloberflaeche,
bling densityof resident particles to be 10. Linford, H.B.
and
E.B.
Saubestre, 37:500-503; 1983
Plaring, 40(4):379-386; 1953 35. Cohen, L E , Plating and Surface Fin-
counted) as well as analytical methods 11.
Linford, H.B.
andE.B.
Saubestre,
such as Auger electron spectroscopyor ishing, 74(11):5841; 1987
Plating. 40(5):489496; 1953 36. Rice, T.,ASTM Bulletin, 178:50;1951
electron spectroscopy for chemical 12.
Linford,H.B.and
E.B.
Saubestre,
analysis. These can, of course, allow Chawla,
37. M.K., Metal
Finishing,
.Plating, 40(6):633-645; 1953 87(9):3 1-32
inferences to be drawn as to the nature 13.
Linford, H.B. and E.B.Saubestre,
ofthesurfacecontaminant,buttheir Plating.40(11):1269-1271; 1953
use is limited to the largest organiza- 14. Ellis, B.N., Cleaning and Confmnina- Biography
tions thathavesuchequipmentinr tion of Electronic Gnnponents and
I house. Assemblies; ElectrochemicalPublica- After majoringinchemistry at Oxford
tions Ltd., Ayr, Scotland, 1986 University and receiving a PhD in e l m -
I chemistry there, Anselm T. Kuhnworked
15. Brandon, N., Electroplating and Metal
CONCLUSIONS Finishing. 28(6):12; 1975 as an electrochemist for Leesona Moos in
16.Lutter, E. Die Enrfettung-Grund- New York and then with John Bockris at
This report will serve to give some lagen, Theorie. Praxis; 2nd ed.. E. the UniversityofPennsylvaniaInthe
idea of the wide rangeof test methods kuze Verlag, Saulgau, 1980 United Kingdom, he was a researcher with
for assessingsurface cleanlinks devel- 17.Cohen.L.E.and JA. Hook. Plating IC1 before starting a career as a university
oped over the years, although it does and 4 u @ e Finishing,, 72(3):70; teacher at Salford Universityandthen
“3985 London University.Heistheauthorand
not claim to be exhaustive. How is a editorofseveral books andover 100
prospective user to choose among 18. Spring,S. et al., Industrial Engineering
Chemistry, Analytical Edition, research publications. Currently he isMan-
them? Clearly, they can be ranked in agingDirectorofFinishingPublications
18:201;1946
teimsofthecost of equipmentor 19. Donelson,J.G. and R.A. Neish.Analyt- Ltd. and Metal Finishing Information Serv-
instruments required to carry out such ical Chemistry, 21:1002-1004; 1949 ices,bothbasedinStevenage, U.K NIF
tests. Then, too, the nature of contami- 20. Pollack, A. and P. Westphal, Introduc-
nationwill affect the choice. Particu- tion to Metal Degreasing and Clean-
late soils are not suited to some of the ing, R. Draper, Teddington, 1963 Write or cull t o h y for our
methods described above, and even in 21. Macnaughton, DJ., Transactions of
terms of oily layers the natureof theoil the Faraday Society, 26~465;1930
22. Morgan, R. and B. Lankler, Industrial
FREE BOOK LIST
can be important. The same questions
Engineering Chemistry, Analytical
affect the issue of testsensitivity.
Edition, 14725; 1942
Metal Finishing
Linford and Saubestre carried out tests
in which the sensitivity of some of the
23. Harris, R, Detergency Evaluation and Three University Plaza
Esting, p. 148,Wiley(Interscience).
simpler methods was compared. What New York Hackensack, NJ 07601
isundoubtedly true is that the ever- 24.Nagakawa, K-. Nonionic Surfitants,
decreasingcostofcomputer-linked Marcel
Dekker,
New York, 1967;
201/487-3700
opticalscanners or camerasshould Shinoda, S., Solvent Properties of FAX 201/487-3705
prompt a reassessment of the methods SurfactantSolutions, MarcelDekker.

METAL FINISHING SEPTEMBER 1993 31


INTRODUCTION
h e common bond that ties
T facets of the metal finishingin-
dustry together is the necessity for
adequate cleaning prior to thea p
plication of the specific coating or
treatment. Countless papers o n
. . _ , . ....
I cleaners havebeenpresented,
telling whatthey are, how they
work, and the variations in operat-
ing conditionsnecessary to pro
duce the degree of cleanliness re-
quired for the specified metal fin-
ishing process.
Technical data sheets describing
proprietary cleaners always have
&ion on control of the cleaner.
This is usually some form of a titra-
tion procedure that, in the case of
alkaline cleaners, measures either
! the free or total alkalinity of the
! procedures thatare not commonly
working solution.
While this techniquemeasures
the concentration of the solution, it
does not measure its effectiveness
as a cleaner, even on initial make
up, for the specific job it has to per-
form, nor does it sense the d e
crease in effectiveness of. the
e load increases.
cleaner a s t hsoil
Unfortunately, the most common
method for determiningthat
cleaning problem exists is the a p
pearance of rejected work be-
cause of variations in surface qual-
itv. irregular coatings, blisters, pits,
streaks. or lack of adhesion. All
these are familiar indications of a
cleaning problem.
Direct measurement of the soil
load in a cleaner is not practical
Since t h e techniques involved are
h e consuming and beyond the
%ope of the industrial metal finish-
ing laboratory. The practical signifi-
Qnce of the results obtained
would be dependent on a single
soil input. a condition which sel-
dom exists.
Obviously, the preferred method maintained so a s to prevent the
all
for measuring the effectiveness of carbon in the steelfrom influencing
the cleaning processis to evaluate the results.
the cleanliness of the actual metal Detection of the small amount of
surfaces that have been cleaned
under specific processingcondi-
tions.
CURRENT METHODS
Many tests have been proposed
for evaluating the cleanlinessof a
metalsurface. Among these are
radioactivecountingtechniques
using a tagged component in the
s o i l to be removed.
a This is a highly specific method
thatdependsonmeasuringthe
cleaner‘s performanceagainst a
s o i l of known composition. It in-
volves specialized equipment and
used in the industry.
The ability ofa n acidified copper
sulfate solution to form a continu-
ous replacement copper coating
on a steelsurface is sometimes
used as a method for evaluating
surface cleanliness. It is of limited
applicatioxand is qualitative rath-
er thwguantithtive.
a Inspection of surfaces under ul-
traviolet light for fluorescent organ-
ic materials is, again, a qualitative
technique.Sophisticatedanalyti-
cal procedurestomeasurethe
amount of surface carbon on steel
test pieces have been advanced
os a preferred method,butthe
equipment is expensive, a n d t h e
area sampled is small.
The test depends upon the con-
version of the small amounts of or-
ganic carbon (present in residual
oils a n d soils together with the car-
bon presentin the smut) to carbon
dioxide in a n oven a t controlled
temperatures a n d in a n oxygen
stream.Operatingconditions are
Finishing83(10): 13-15.
Repnnted with permission from
Elsevier Science Inc.
carbon dioxide generated requires
special procedures. While carbon
is a prohble component of most
metal surfacesoils, there is no guar-
a n t e e of this being true, anda sur-
face showing low carbon does not
necessarily indicate a clean sur-
face.
Physical methods have beenad-
vanced that attempt to measure
the ability of a drop of pure water
to wet a cleaned surface. These
techniquesmeasurethecontact
angle between the drop a n d the
surface or the height and/or diame-
ter of a drop of water of known vol-
ume on the surface. Again, these
proceduresrequire
specialized
equipment and are more suitable
for the research laboratory thanfor
a production control laboratory.
By far, the most common test for
surfacecleanliness is the“water
break“ test. A visual evaluation is
m a d e of the ability of water to wet
the cleanedsurfacecompletely
without pulling back to form beads
of water a n d leavingunwetted
areas. Whenproperlyperformed,
the test should be conducted after I
the test piece has b e e n acid
dipped a n d rinsed to remove the
I
last traces of any residual alkaline
cleaner thatwould influencethe re-
sults.
Obviously, thisis a go. n o g o .
type of test that establishes
o n e lev-
el of cleanliness as being accep
table for all metal finishing proc-
esses. It does not takeinto account
the fact that certain processes re-
quire a higher degree of cleanli-
ness than c a n be detected by this
test while other processes may be
 -
performed successfully at a lower
degree of cleaning efficiency.

BACK TO BASICS
When asurface is cleaned by
either physical or chemical meth-
ods, or a combination of the two,
the net result is an increase in sur-
face energy and a measureof
surface energy is a direct measure
of cleanliness.
In the liquid phase, surface ten-
sion is a direct measure of surface
energy. Therefore,a comparison of
the surface energy of a metal sur-
face with the surface tension of a
liquid, yields a direct measurement
of surface cleanliness.
In practical terms, if a drop of liq- Fig. 1. Surface tension of res? solution Fig. 2. Surface tension of test sol&,
uid of knownsurfacetension is is less than surface energy of is greater than surface energy
metal.Solution spreads into ir- metal. Solution retainsbead fa
placed on ametalsurface and regularpattern. and doesnot spread.
that liquid wetsthe metal Surface
and spreads as shown inFig. I . this
indicates that the surface energy of
the metal is greater than the sur- been cleaned. centimeter. The composition. QI
face energy of the liquid.
The use of graded sets of liquids shown in Table I.
.
properties of the test solutioW.9
::.,
. ...
Conversely, if the drop of liquid of
known surface tension remainsaas of known surface tension hasbeen The ethanol values are
4 .

bead and does notspread. as used in the p a s t to measure the sur- anhydrous ethanol. Reagent83
shown inFig. 2, then the surface en- face wettability of plasticsand met- potassium carbonate was Usc
ergy of the metalis less than the sur- als a s well asmetal cleanliness, but and solutions were prepared ush
face energyofthe liquid. {
they have been limited to surface deionized water careftj in
tension at or below that of water. cleaned glassware.
A graded seriesofliquidsof
known surface tension can there Thetest procedureherein de- The apparent surface tense
fore be used to measurethesur- scribedextendsthis rangeto inq were measuredby the ring mettu
face energy of a metalsurface, clude surface tensionabove that of depicted in Fig. 3 and correct
and therefore its cleanliness, b y o b pure water and arranges the sur- specific gravity using standc
servingwhetheror notthe liquid face tension of the test liquids ina rocedures.The solutions bad;
wets and spreads on the dried sur- geometric progression of 11 steps tassium carbonate were t r
d
face ofthe actual part thathas-. ". fro'& about 25 to 100 dynesper ith activated carbonand filten

Table I
~~~ ~~ ~~ ~

Composition Apparent Corrected

Solution % by Volume Surface Tension Surface
Specific Tension
Number Ethanol Dl water Dyneslcm Gravity Dyneslcm
~~

80.0 20.0 27.2 0.850 24.5

51.O 49.0 31.2 0.922 28.2
33.0 67.0 36.0 0.955 32.7
21.5 78.5 41.9 0.970 38.4
85.7 14.3 47.3 0.978 43.7
90.7 9.3 53.4 0.985 49.7
95.5 4.5 61.3 0.991 57.6
1.o 99.0 70.1 0.995 66.6
g/L Potassium Carbonate
8 220 80.0 1.171 75.8
9 520 91.2 1.377 86.3
10 800 106.7 1.535 101.2
;ins require no addltlonal fie&-
merit,
me solutions should be stored ir:
clean glass containers. Smallglass
wttles with a glass medicine drop
per closure are convenient foruse
in performing the test.
TO perform the test, the surface
should be processed through the
Cycle.rinsed, and then
driedwith 0 Current Of Clean air.
Mthout delay, a drop or series of
drops of one of thetestsolutions
are placed ona horizontal surface
of the test piece noting whether it
wads or spreads.
mere is no need to be con-
cerned withcontact angleor drop
kt height. If thedropletbeads,
move to the next lower numbered
glutiop and continue moving
awn one number untila solution is Fig. 3. Measuring surface tension to calibrate test solution.
leached that
wets
the
surface
,pontaneously.
Theresults are reported as the
(owest numbered test solution that
an be made to bead on the sur-
face. In evaluating a large area,
check a number of different loca
tions as the degree of cleanliness
will vary fromarea to area.

CONCLUSION
Thistest represents a practical.
rapid, economical and sensitive
method for the metal finisher to:
1, Control the present cleaning
procedures.
2. Monitorthe "life"of cleaners.
3. Evaluate competitive processes.
4. Screen incoming surfacesfor
"difficult to clean" soils. MF

Blography

William Jones is
research director
Heatbafh
of
Corp. He has
i.. worked
for 35
years as a chem-
ist specializing in
the development
metal
surface
teafing processesincluding clean-
@% Conversion coatings,and molt-

ensalt formulations.
Unltad States Center for Envlronmental
Offlce of Solld
Waste
Envlronrnental Protectlon Research lntormatlon and Emergency Response
Away

SolventWasteReduction
AlternativesSeminar
SpeakerPapers

Minimization of Process Equipment Cleaning

Waste
 MINIMIZATION OF PROCESS EQUIPMENT CLEANING WASTE

Carl H. Fromm
Srinivas Budaraju
Susanne A. Cordery

Jacobs Engineering Group Inc.

HTM Division
251 South Lake Avenue
Pasadena, California 91101

ABSTRACT

Thewasteassociatedwithcleaning of processequipment is probably a significant

contributor to the total waste volume generated by industry. This paper addresses the
following aspects related to equipment cleaning waste generation:

o Review of reasonsforcleaning process equipment

o Reduction of cleaningfrequency
o Reduction of quantityandtoxicity of cleaningwaste
o Costs
associated
with
cleaning

Equipment cleaning techniques, media, and their applications are reviewed. Reduction
of cleaningfrequency terms of inhibition offoulingthroughproper
is addressedin
squipment
design and operation,
maximization of equipment dedication,
proper
productionscheduling,andavoidance of unnecessarycleaning. When cleaning has to
beperformed,thequantityandtoxicity of resulting waste can beminimized by
reducing clingage, amount of cleaning solution, choice of. less toxic cleaning solution,
cleaningsolutionreuse,andotherapproaches.Applicationexamples are givento
illustrate each approach.
 E

INTRODUCTION

The current costs of waste disposal and treatment, regulatory pressure, and concerns
about legal liabilities have been forcing (J.S. industries to scrutinize their hazardous
wastegenerationpractices i/. A primaryobjective of t h e s ee f f o r t sh a sb e e nt o
minimize waste generation, i.e. to reduce the quantity and toxicityof the waste.

Of the many industrial waste-generating operations, process equipment cleaning (PEC)

is nearlyuniversalin its application, as it is practiced in all segments of manu-
facturingindustry. PEC is of particularimportancefordiscreteprocessessuch as
batchreactions,compounding,surfacecoatingoperations, etc. This is becausethe
cleaning frequency for discrete processes is generally much higher than for continuous
processes.
However,
this does not
mean t h a t cleanup
wastes
from
continuous
processes can be ignored. Disposal of sludges from cleaning o f heat exchanger fouling
deposits,forexample, is oftenofconcerntotheoperators of petroleumrefining,
petrochemical and chemical process facilities,.

The intent of this paper is to review basic waste minimization strategies applicable to
cleaningoperations.Theintent is toprovide a structuredclassification of such
strategies presented in the form of a prototype checklist which can be used to help
focus and plan a concerted attack on waste.

WHY EQUIPMENT IS CLEANED

Equipment cleaning is a maintenance function typically performed for the following

reasons:

- t o restore or maintaintheoperatingefficiency of equipment, e.g., to

restore
adequate
heat
transfer rate and low pressure drop in h e a t
exchangers.
- to avoid or limitproductcontamination, e.g., when a paint mix tank needs
to be cleaned between batches of varying paint formulations.
- tominimizecorrosionandextendequipmentlifetime.
- toallowforinspectionandrepair of equipment.
- toimproveappearance(exteriorsurfaces only).
 "

Theneedforcleaning is a directconsequence of depositsformedonthesurfaces

exposed to the process environment. Some of the major routes and origins of deposit
formation are summarizedinTable 1 alongwithdescriptionsandsomeexamples.
Understanding how andwhythedeposits are formed is a critical f i r s t s t e p inany
wasteminimizationeffort.Itisanespeciallyimportantaspect for equipmentand
process designers, because the need for equipment cleaning can often be reduced or
eliminated through design rnodifications at minimal expense during the design stage.

A common sense approach to minimizing waste from equipment cleaning operations is

to pose and answer t h e following sequence of questions:

- why is the depositpresent?

- how can
cleaning
be
curtailed or avoided (i.e., cleaning
frequency
reduced)?
- when
cleaning is necessary,
which
cleaning
method
and
medium
will
generate the least amount of least toxic waste?

Sections below address major aspects related to the last two questions.

REDUCTION OF CLEANING FREQUENCY

Generally,theneedforcleaningcan be reduced or avoidedaltogether by t h e

application of the following measures:

- inhibition of fouling or depositformation rate.

- maximizingdedication of processequipmentto a singleformulation or
function.
- proper
production
campaign
scheduling.
- avoidance of unnecessary
cleaning.

Inhibition -
of foulinq is of particular importance in h e a t transfer applications where i t
can be accomplished through a variety of means, including use of smooth heat transfer
surfaces, lower film temperatures, increased turbulence, control of fouling precursors
and proper choice of exchanger type.
 E

" TABLE 1. TYPICAL ROUTES AND ORIGINS OF DEPOSIT

FORMATION IN PROCESS EQUIPMENT

~~

Route/Origin Description

Crystallization Major problem in evaporators and

crystalizers (e.g. very frequent in
food processing).

Sedimentation Major problem in petroleum refinery

crude unit desalters and oil storage
tanks. Also present in cooling tower
basins.

ChemicalreactionsandpolymerizationBuildupon t h e internalreactorsur-
faces are often encountered (e.g. allyl
chloride synthesis). Also of importance
in crude oil storage tanks.

High temperature coking Carbonaceous material depositing on

walls of furance tubes (e.9. f u r n a c e
for ethylene chloride pyrolysis).

Corrosion Common problem in heat exchangers in

chemicals and allied products industry.

Bacterial growth (biofouling) Major problem on cooling-water-side

of heat exchangers in electric power
production.

Clingage Residual coat of process liquid l e f t

(of importance to solvent
cleaning applications)
after drainage; major problem in
reactors and mixers in the paint
manufacturing industry and generally
in all high-viscosity liquid transfer
operations.
The USE: af smoothheatexchangersurfacesresults in loweringtheadhesion of the
deposit o r its precursor to t h e surface. Application of electropolished stainless steel
tubes in a forced circulation evaporator used in black liquor service in a papermill
resulted in a dramatic reduction of cleaning frequency from once a week to Once a
year 2. Smoothnon-sticksurfacescanalsobeprovided by Teflon (a registered
trademark o f E.I. DupontdeNemours & Co.). Teflonheatexchangerdesignsare
commerciallyavailable,as are designsutilizingTefloncoatedsteel. In a s e p a r a t e
application,condensersusingTeflon-coatedtubeshavebeenshowntodrastically
reducefoulingandresistcorrosionwhilemaintaining high thermalefficiency.The
higher cost of material was weighed against reduced energy cost to show a 69 percent
return on investment in the f i r s t year before tax GI. If reduced cleaning costs were
to be added, t h e ROI would have been higher.

The rate of heat exchanger fouling in a given service is dependent upon fluid velocity
and, quite often,onfilmtemperature.Filmtemperaturecontrolsthespeed of
chemicalreactionswhichresultindeposit-formingcompoundswhilefluidvelocity
controls the shear rate at the fluid-deposit interface.

Hence,loweringthetemperature of theheatingmediumandincreasingthefluid
velocity (e.g. by recirculation) can produce a desired reduction of the fouling rate. An
economic trade-off analysis between the increase in pumping cost and the decrease in
t h ec o s t of cleaningandotherpossiblesavingsappearswarrantedininvestigations
relating the degree of -oversizing to cleaning waste generation. A general review of
thermal
andhydrodynamic
aspects of heat
exchanger
fouling
was
provided by
Knudsen 11.

Control of depositprecursors is .oftenanobviouspracticalconsideration.Proper

maintenance of coolingwaterqualityinopencirculatingsystems is of paramount
importance to water-side heat exchanger fouling. Control of hardness, pH, corrosivity
and
biofouling
tendency is accomplished
through
careful
monitoring
of
water .

quality 201. In particular,biocidesaddedintreatmentmustpropagatetheentire

coolingfluidpathinordertobedepositedandfunction at all locationsinthe
exchanger;andacidfeedequipmenttomaintainthe pH in thenon-scalingrangeof
6 to 7 must be reliable or else rapid scaling or corrosion problems occur 11.

Thechoice of heatexchangertypecaninfluencecleaningfrequency. For example,

spiral plate exchangers are often specified over other designs in fermentation plants,
 "

owing
to t h e e a s e of solid resuspension,
absence o f pockets,
andnon-plugging
characteristics.Rodbaffledesignprovidesmoreeffectiveshell-sideturbulence at
lowerpressuredropcomparedto a moreconventionalsegmentedbaffledesign.
Therefore, t h e rod baffle design can be expected to exhibit superior shell-side fouling
characteristics.

Slowing down the rate o f deposit formation is not limited to heat exchangers, but also
is importantforothertypes of equipment. For example,crude oil's exposureto
atmosphericoxygencan cause formation of gumsandresinsduringlongexposure
periods inside storage tanks. The use of floating roof tanks or inert gas blanketing has
beensuggested.as a waytoreducetankdepositbuildup !!I. Similarly,inpaint
manufacturing, exposure to air causes formation of solid films that adhere strongly t o
t h e internal surface of t h e mixers.Thiscanbeavoided by using closed storage and
transfer systems, as evidenced by experience a t Ford Motor Company. At Ford, the
paint storage and transfer system was enclosed and redesigned for full recirculation
resulting in less frequent and easier cleanups and an improvement of paint quality 21.
Otherapplications of foulinginhibitionincludecoating of reactorinternalswith
special chemicals to prevent scale formation. These practices have been used in t h e
suspension polymerization process for polyvinyl chloriae 61.

Maximizinqdedication -
of processequipmentto a singleprocessfunction or
formulation will reduce cleaning frequency, as the frequency of switching to different
formulations will diminish. Maximum dedication means either converting from a batch
t o a continuous process or using the equipment intermittently j u s t for one formulation.

Historically, the changeover from batch or cyclic to continuous operations has been
common in t h e chemical industry, .owing to increased product demand, increased labor
costs and technological progress. The advantages of the continuous process over batch
include the ease of automation and control (which minimizes human error leading to
inferior product quality) and lower labor requirements.

The choice between the continuous or batch mode is governed primarily by production
volume and related trade-offs between capital and operating costs. The batch process
is advantageous in situations where production volumes are small and product diversity
large.Batchprocess,eshaveprovenadvantageous even for certainlargevolume
products, such as, neoprene rubber and phenolic resins, where continuous alternatives
were developed but failed to find wide application u/.
Dedicating a piece of equipment to a singleformulationinthebatchprocessmeans
t h a t t h e equipment
remains
dormant
between
individual
production
campaigns.
Cleaningaftereachcampaigncanbeavoidedprovidedthatmaterialsleftinthe
equipment do notdeterioratewithtime or corrodetheinternals.Also, t h e cost
penalties associated with equipment under-utilization must be outweighed by cleaning
costs incurred when the equipmentis used with more than one formulation.

Properproductionschedulinq is a commonlyinvokedmethodtodecreasecleaning
frequency.Equipmentutilizationstrategiesandtheresultingproductionschedules
shouldbederivedthroughoptimizationanalysis,wheretheobjective is t o m e e t t h e
desiredproductiongoalswithdueconsideration of suchconstraints as available
equipment,cost o f turnaround,laboravailability,storage, etc. Meetingproduction
goals is tobeaccomplishedwithminimumcost,whichincludesminimization of
cleaning frequency. A general review of optimum strategy formulation was given by
Peters and Timmerhaus !/.

However, in a typicalsituation a formaloptimizationanalysis is notusedoften.

R a t h e r , a common-sense approach to production scheduling is used based on trial-and-
error preparation of production bar-charts. To reduce cleaning waste, i t is generally
desirable to schedule long campaign runs, as opposed to short and more frequent runs.
Productionschedulers now mustbeawareofthecurrentwastedisposalcosts,an
a s p e c t that previously could have been ignored.

Avoidance -
of unnecessary cleaninq should be one of the goals of waste minimization
audits.
Attimes,
equipment
cleaning
is
performed
routinely
with
little or no
consideration of therationale f o r thecleaningactivity. An actual case is known
where a ball mill was used periodically to wet-grind a certain powder.Theball mill
with corrosion-proof internals was totally dedicated to the same formulation, a stable
mixture of inorganicpowders.Yet,theballmill was cleaned after each use for no
apparent reason. Upon questioning,. the only justification provided was that the other
non-dedicated ball mills at the facility were cleaned after every use.
REDUCTION OF QUANTITY AND TOXICITY OF CLEANUP WASTE

When cleaning has to be performed, it should be performed effectively with minimal

generation of waste.Typicalconsiderationsincludethechoice of cleaningmedium,
cleaning technique and waste disposal option. A brief overview of these choices (with
the exception of waste disposal), is provided in the following paragraphs.

A distinctioncan be madebetweenchemicalandmechanicalcleaning.Chemical
cleaningrequiresthe use of substancessuchasthoseshown in Table 2 which are
employed to chemically attack the deposits and render them either solvent or water-
soluble. The basic reaction types include oxidation, reduction, chelation or conversion
of insoluble oxides into soluble salts. Cleaning formulations also include surfactants to
lowersurfacetension of solutiontoallowforfasterpenetrationandbreakup of
deposits.

Physical -
or mechanical cleaninq relies on breaking the adhesion of t h e d e p o s i t t o a
surface using mechanical devices, such as scrapers, squeegees, rags, drag lines, "pigs",
lances or through the use of high
velocity
water jets (hydroblasting).
Often
mechanicalandchemicalcleaning are combined, e.g., when high velocity jetsare
employed with caustic solutions to attack depositsin paint mix tanks.

According
to a classification
developed by Loucks 10/, six
separate
cleaning
techniques are distinguished:

- fill-and-empty
technique
- circulation
technique
- "flow
over"
technique .

- gas
propel
technique
- process
simulation
technique
- onstream
cleaning
technique

In the "fill-and-empty"technique, a process vessel is isolated from other equipment

andfilledwithanappropriatecleaningsolution.Thesolution can beheatedand
agitated and, after a period of 4 to 8 hours i t is drained. Rinse-water or diluted alkali
or acidsolutions are thenusedtoremoveresidualcleaningchemical.Drained
chemicalsandsubsequentrinses are eitherreused,treated,recycled or land-filled
 i;
r)
al

Y
m

.-0
I

ob

5 n
a
a c

-0
m
.
.d

L -0
0 0
I
c
m
i
0
0
L
-0

f
E

"

dependingon
their
composition
and
the
availability
of
disposal
options
at
the
particular site. The method uses large quantities of chemicals and requires substantial
downtime. I t is typically applicable to small vessels, tanks or heat exchangers.

In t h e "circulation" technique, the vessel is filled with cleaning solution to an overflow

andallowedtostand for a short time period, after which the solution is circulated
with an auxiliary pump. Fresh make-up solution can be pumped in i f used solution is
withdrawn. In boilers,nitrogengas is used toprovideagitationformoreeffective
scale removal.

The"flowover"techniqueconsists of spraying t h e solutionontothe surface. It is

applicabletolarge tanks wherecleaning by filling or recirculationwouldrequire
excessive
quantities of cleaning
solution.
Extra
safety
precautions are usually
neces'sary.

The"gaspropel"techniqueutilizescleaningagents t h a t are not overly corrosive at

highertemperatureswhensteam is usedtopropelthemthroughthesystem.This
technique is useful for pipelines,whereinhibitedorganicacids or chelants are
entrained into a f l o w of steam which carries the liquid drops and solids debris through
hydraulic obstacles of the system.

The ''process simulation" technique is applied t o e q u i p m e n t t h a t is easily fouled and

wherespareparallelunits are provided.Fouledequipment is cleaned by simulated
process operation, where the equipment is isolated, drained of process fluid and filled
withthecleaningsolutionusingprocesspumpsandcontrolstomaintainflowand
temperature. An example is removal of iron oxideandcopperdepositsfromhigh
pressure steam generators using ammoniated EDTA solution.

The "onstream cleaning" technique is probably the most preferable method, as i t relies
on
process
fluid
to do the
cleaning
during
normal
operation.
Often
auxiliary
mechanical devices are used along with additives, such as EDTA or a c i d s t o p r o m o t e
deposit removal. This technique is used for cleaning reactor jackets, gas compression
stationengines,heatexchangers,andotherequipment.In-servicecleaning of large
circulating cooling water systems is often done through intermittent pH swing to the
acidside of neutralandbackagain.Amongmanymechanicaldevicesusedin
conjunctionwithonstreamcleaning,onecouldmentionram valves forroddingout
 pluggednozzlesandmoveableheatexchangertubeinsertspropelled by reversing
-
process fluid GI. In a separate example, the use of fluidized beds of inert solids (e.g.,
sand) was found useful in heat transfer applications characterized by extreme fouling,
such as heatrecoveryfromgeothermalbrines.Solidparticlesconstantlyabradethe
deposit away from the heat transfer surface, maintaining high transfer rates.

The choice of cleaning method and media, apart from cost, should also be based on t h e
following environmental considerations:

- minimize t h e amount of cleaningsolutionused;

- choose the mediumultimatelyresultingintheleasttoxicwaste;
- determine ahead of t i m e how the cleaning waste is going to be disposed of.

The use of chemical

cleaning (e.g., with
mineral or organic
acids)
results
in
apbreciable quantities of hazardous cleaning wastes which need to be treated prior to
disposal. As appropriate treatment facilities are not available onsite in every case,
mechanicalcleaningandonstreamcleaningappearpreferabletochemicalcleaning.
Accordingtoinformationobtainedfromvariouscleaningcontractors,thesefactors
are gainingrecognition as the recent trend has been more toward hydroblasting and
onstream cleaning and away from chemical cleaning. This was attributed to the rising
costs o f waste disposal and treatment.

When chemical cleaning is unavoidable, the least toxic medium should be chosen; for
example,analkalinecleanerwould be preferableover a halogenatedsolvent. How-
ever, if the toxicity of the "soil" to be removed is the controlling factor, the cleaning
I
agent with a higher potential for recovery and reuse should be used.
I

I An attractive
alternative
those
to cleaning
methods
that
require
disassembly of
equipment for cleaning, is a clean-in-place (CIP) system. The system is composed of
tanks,
heat
exchangers,
filters,
pumps,
piping
and
instrumentation
permanently
installed as an auxiliarysystemdesigned to circulate a controlledinventory of
cleaning solution through isolated process equipment often using spray manifolds or
liquid jet nozzlesinsideproductionvessels.The CIP systemsgenerallyreducethe
usage of cleaningmedium.Theyareespeciallyeffectivewhencoupledwithhigh
velocityautomated jet manifoldsandstagedcounter-currentrinsing;an 80 . t o 90
percentreduction in aqueouswastewasachieved by paintmanu'facturersafter
 "

installing high pressure spray nozzles for tank rinsing s/.CIP systems are popular in
food, pharmaceutical and paint industries; however they are utilized less frequently in
the chemical processing industry z/.
Reuse of cleaningsolutions is common in CIP systems. In general, reuse of cleaning
solutions is highly desirable, especially if they can be utilized as p a r t of formulation.
For example, a considerablereduction in reactorcleanupwastewasachieved by
BordenChemicalwhereatwo-steprinsesequencewasappliedto a b a t c hk e t t l e
arrangement used for phenolic resin synthesis. The first rinse used a small amount of
water generating a concentrated stream which could be recycled to the process. The
secondfullvolumerinsegeneratedwastewaterwithamuchlowercontent of toxic
material than a previously used single rinse method g/.
Other examples include reuse
of rinsewaterfromlatextankcleaning as p a r t of latexformulationinthepaint
industfy E/ and use of warm oil for flushing the deposits out from crude oil s t o r a g e
tanks in an oil refinery, followed by solids separation in the slop oil system x/.
The preceding sections were concerned with reduction of qleaning frequency and with
the choice of the least waste-intensive cleaning methodology. There is a related, but
independentaspect of cleaningwastereduction, i.e., reduction of clingage. As
explained previously, clingage is the amount of process material left inside the vessel
or other equipment after draining. In operations involving viscous fluids, such as paint
manufacturing and resin compounding, clingage is an important consideration as i t not
only results in waste'which is expensive to dispose of, but also represents a d i r e c t loss
of product or raw material.

To reduce clingage, the following measures should be considered:

- provision of adequatedrainage time;

- useoflow-adherencesurfaces, e.g., fluorocarbon or electropolishedsteel;
- useofmechanicalwallwipers(dual shaft mixers);
- use ofmanualwipers or squeegees;
- choice
of
square
cylindrical or sphericalgeometry to minimizewetted
surface;
- rotation of agitator after batch dumping to reduce clingage on the blade.
 All of t h e- above measures are self-explanatory and do not require elaboration. ~~~t
are practiced extensively throughout industry. The use of tank linings as a means o f
reducingadherenceandpreventingcorrosionhasbeenaddressed by Zolin E/and
Kays GI. The use of dual shaft mixers with slow scraper blades wiping the walls and
t h e bottom of mixing tanks is common in applications involving viscous liquids E/.

COST OF CLEANING

The cost of cleaning can be viewed as being composed of the following elements:

Direct Costs
- equipment
assembly/disassembly
- cleaning
chemicals
andsupplies
- waste
treatment
anddisposal
- cleaning
labor
and
supervision
- cleaning
equipment
depreciation
- utility costs

Indirect Costs
- planning
and
scheduling
- cost of lost
production
- c o s t o f lostrawmaterialsinventory
- inspection
and
testing
- process
equipment
deterioration

Oftenequipmentcleaning is performed by outsidecontractorswithspecialized

equipment who assume the responsibility for hauling away the waste and for disposing
of it properly.

Costs of cleaningvarywidelydependinguponthemedium,methodandapplication.
Recent inquiries into t h e c o s t of cleaning of heat exchangers established the following
compilation of relative heat exchanger cleaning costs using contracted service:

c
Cost Relative Method
Hydroblasting 1.0
Rodding 4 to 5
Chemical Cleaning:
Without
waste
disposal 0.3 t o 3
disposal
waste
With 2.1 t o 4

In many cases the cost of cleaning (taken as direct cost only) is lumped together with
other maintenance costs. As a result, plant management may not have good visibility
of t h e actual costs of cleaning,whichmayimpedemanagement'ssupportforwaste
minimization
efforts.
Often,
when
plant
management
learns of the true c o s t
dimension, action to lower cleaning costs is quickly initiated.

SUMMARY

As mentioned in the introduction, the intent of this paper is to provide a brief review
of techniques, approaches and strategies for minimizing equipment cleaning waste and
toprovide a classificationschemethat may serve as an initialguidetothose
interestedinwasteminimization.Such a classification or summary is provided in
Table 3. Thisserves as a prototypechecklistforaddressingallwasteminimization
issues in a logical sequence.

The subject of equipmentcleaning is quitediverse as thefunction is performedin

virtuallyeveryindustry.Generalizationspresented in thispapermustbetranslated
into site-specific and exacting requirements in any waste minimization effort.

ACKNOWLEDGEMENTS

The authors wish to expresstheirgratitudetothe U.S. EnvironmentalProtection

Agency, O f f i c e of Solid Waste, for their support in developing a substantial portion of
the material presented in this paper.
 TABLE 3. WASTE MINIMIZATION OF EQUIPMENT
"

CLEANING WASTE - SUMMARY OF APPROACHES

1 WHY IS DEPOSIT PRESENT? I

REDUCE CLEANING FREQUENCY

1. Inhibition of fouling r a t e
- smooth heat transfer surfaces
- lower film
temperature/higher
turbulence
- control of fouling
precursors
- choice of heatexchanger type
2. Maximizeprocessequipmentdedication
- conversionfrombatchtocontinuousoperation
- dedication
to
single
composition
3. Proper
production
scheduling
4. Avoidance of unnecessarycleaning

REDUCE QUANTITY AND TOXICITY OF WASTE

1. Minimizeamount of cleaningsolution
- high
pressure
nozzles
- flow-over technique
- on-atream
cleaning
- use of CIP systemswithstaged or counter-current
rinsing
- reuae of cleaning
solution
2. Minimizetoxicity of spentcleaningsolutions
- clingage
reduction
- mechanical(hydroblasting) over chemicalcleaning
1. League o f Women V o t e r s of Massachusetts, Waste Reduction: The Untold Story,
Conference held June 19-21, 1985 at National Academy of Sciences Conference
Center, Woods Hole, Massachusetts.

2. Uddeholm
Corporation (Sweden), Technical brochure on Tubec Tubes and
communications with AvestaStainless Inc., Totowa, New Jersey

3. Knudsen, J.G., FoulinqofHeat Exchangers: Are We SolvinqtheProblem?,

Chem. Eng. Progress, Feb. 1984, pp. 63-69.

4. Jacobs EngineeringGroup Inc., AlternativesforHazardous Waste Manaqement

Practices in the Petroleum Refining Industry, EPA-530-SW-l72C, Washington,
D.C., U.S. Environmental Protection Agency, 1979.

5. Colleta, V., Powers, J., Chem Proc. 44(4):20-1, 1981.

6. Cameron, J.B., Lundeen, A.J., McCulley, Jr. J.H., Hydroc. Proc., 59(3):39-50,
1980.

7. Euleco S.P.A., Euleco Continuous Process: Technical Bulletin, 1975.

0. Shell International Research Inc., Brit. Patent No. 136, 189; issued Dec. 11, 1968.

9. Peters, WE., Timmerhaus, K.D., Plant Desiqn & Economics

for
Chemical
Enqineers, 3rd Edition, McGraw Hill Book Co., 1980.

10. Loucks, C.M., Boosting Capacities with Chemicals, Chem. Eng. (deskbook issue),
80(5):79-84, 1973.

11. Water Services o f America, Inc., Superscrubber Technical Bulletin, 1985.

12. U.S. Environmental Protection Aqency, Office of Water & WasteManaaement:

DevelopmentDocument'forProposed-Effluent Guidelines, New Source Per:
forrnance Standards and Pretreatment Standards for thePaintFormulatinq,
Paint Source Cateqory, EPA-440-1-79-0496, Washington, D.C., 1979.

13. Hyde, J.M., New

Development in CIP Practices, Chem. Eng. Progress
81(1):39-41,
1985. .

14. Huisingh, D., et. al., Proven Profit from Pollution Prevention, The I n s t i t u t e f o r
Local Self-Reliance, Washington, D.C., 1985.

15. Riley, J.E., OevelopmentDocument for E f f l u e n tL i m i t a t i o n Guidelines, New

Source Performance Standards for the Tire and Synthetic Segment of the Rubber
Processinq Industry, Point Source Cateqory, EPA-440-1-74-013A, U.S. Environ-
,mental Protection Agency, 1974.

16. Barnett, J.W., Better Ways to Clean Crude Storaqe Tanks and Desalters, Hydroc.
Proc. 60(1):82-86, 1980.

17. Zolin, B.I., Chem. Proc. 47(9):63-5, 1984.

 "

REFERENCES (Continued)

i8. Kays, W.B., Construction o f Lininq for Reservoirs,Tanks & PollutionControl

Facilities, Wiley, New York, 1979.

19. MyersMixingCompany:privatecommunication, 1985.

20. BetzLaboratories Inc., Handbook of Industrial Water Conditioninq, 8th Ed.,

Trevose, Pennsylvania 1980.
United States Office of Research and EPA/625/R-93/016
Environmental Protection Development February 1994
Agency Washington DC 20460

Guide to Cleaner
Technologies

Alternatives to Chlorinated
Solvents for Cleaning and
Degreasing

Available Technologies for Alternatives to

Chlorinated Solvents for Cleaning and
Degreasing: Descriptive Aspects and
Operational Aspects
 L
P

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3
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 . . . .
m

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10
E
 KNOW YOUR CLEANING ALTERNATIVES

Note: Thefollowing glossary of cleaning alternatives is provided for reference and

definitive purposes only and is not intended as a promotionof any spec@ chemistry,
product or technology.

ALCOHOL BASED CLEANING (AL)

These alternatives have found use in the electronics industry as CFC alternatives and
areas requiring high degrees of cleanliness. Limitations to use are explosive risks, toxicity and
emissions concerns. Benefits are quick parts drying time and low residuals.
Examples of alcohols used include: ethanol, methanol, isopropanol, and glycol.

AQUEOUS BASED CHEMISTRIES (AQ)

A.k.a. Water Based Chemistries, these fall largely into the alkaline, and acid families with
other groupings containing surfactants, emulsifiers and detergents. Changing over to a water
based cleaning operation will of course result in some increase in water discharge. Many
technologies exist to separate the water from
the spent cleaners for reuse in make-up of new
chemical baths. Drying time of parts may increase and therefore problematic for work that tends
to rust quickly.

HYDROCARBON BLENDSWB)
Hydrocarbon blends seek to fill the market of drop-in alternatives to chlorinated solvents
and CFCs. Many offer a quick changeover using existing tanks and equipment. Caution should
be exercised is choosing a blend to make sure
the components are not scheduled to be phased out
or banned. Many blends have excellent cleaning abilities with some reduced risk to workers.
The SARA TitleI11 list should be consulted to determine if the chemical is regulated.

NON-AQUEOUS CHEMISTRIES (NA)

This category distinguishes these alternatives from their water based counterparts, though
many of these alternatives have water as a component. They often clean more aggressively than
their water based counterparts. The toxicity of some of these alternatives has not been
completely determined. Some are listed under theSARA Title I11 reporting.

NON-LIQUID ALTERNATIVES (NL)

This category covers all types of solid stripping media suchas C02 pellets, plastic blast
media, sponge pellets, anddry ice flakes, Also included are super critical fluids alternatives.
The blast media are excellent for cleaning large parts and simple geometries. Delicate
to these applications. Super critical C02 has been
instruments and blind holes are not well-suited
used successfully on small to medium sized applications. Capital costs for installing the pumps
and high pressure vessels has prohibited it's wide-spread usage.

TERPENE / SEMI AQUEOUS CHEMISTRIES (TP)

Terpenes have found a wide variety of uses in the electronics industry and cleaning parts
with complex geometries. They are often coupled with ultrasonic or similar agitation devices.
The long term toxicityof terpenes and other pine and citrus derivatives remains a matter of

Anonymous. 1994. Know Your Cleaning Alternatives. The Catalyst 1(2):4-5. Reproduced with permission from the New Jersey Technical
Assistance Program, Newark, New Jersey.
 study. Early varieties tended to have low flash points; a problem that has been well addressed
by
today's chemical vendors.
Examples of terpene include d-limonene, a terpineol derivative extractedfiom citrus
fiuit.

CIRCUIT BOARD CLEANING SYSTEMS (BC)

This category is important to high tech industries. Vendors sell these chemistries
as low
solid fluxes and no-clean fluxes.

CUSTOM DESIGNED SYSTEMS OS)

These are large conveyorized or monorail cleaning systems. The entire system can be
tailored to the facilitieswork centers and parts flow. Because of the substantial cost, a thorough
survey of cleaning practices that establishes that there is a need to clean is urged. Process and
chemical modifications may reduce or eliminate the need for cleaning, thereby saving capital.

IMMERSION TANKS (IT)

. Immersion tanks come in a wide range of sizes and are often coupled with agitation or
ultrasonics, which reduces the need for a highly aggressive solvent that might damage the work.

ROTARY PARTS WASHERS (RW)

These systems are designed to function similar to large washing machines and dish
washers. Most are of the cabinet variety with a turntable in the center to spin theasparts
Rotary washers can also help
cleaning jets direct the solvent onto the parts or baskets of parts.
dry parts by spinning the liquid off or blowing offitwith compressed air.

SPRAY WASH SYSTEMS (SW)

Very similar to Rotary Washers, these may even contain a rotating basket within an
immersion tank. Spray wash systemswork by agitating parts and forcing solvents into blind
holes and difficult geometries. They may not be useful for delicate instrumentation
or sealed
components where sprays might damage the parts.

ULTRASONICS (US)
Ultrasonic cleaning systems work through generating high frequency vibrations which
cause the detergents to actively collide with the parts and soils.
This impaction lifts the dirt and
carries it awayfrom the parts. Ultrasonic systems work well in most applications with two
exceptions; part'orientation with respect
to the ultrasonic generating unit may cause shadowing,
or zones of less aggressive cleaning; and electricity costbewill increased proportional to use.
Therefore, large scale application may resultin a significant increase in power demand.
 Fact Sheet
ENVIRONMENTAL SERVICES DIVISION
State of Michigan Departments of Commerce and Natural Resources

AQUEOUS AhJD SEMI-AQUEOUS CLEANERS

INTRODUCTION
The traditionalway to cleanan oily
part was to dip it in a solvent or
suspend it in solvent vapors. It was
fast and effective. Today, however,
the liabilities associated with worker
safety &d management of hazardous
wastes and restrictionson
production of some chlorinated
solvents are motivating businesses
to find alternativesto solvents in
their cleaning processes. Aqueous
and semi-aqueous cleanersare being
advertised by their manufacturersas
reliable substitutesfor solvents in
many different cleaning
applications. Businesses have many
questions regarding these
substitutes. Are they effectivein
cleaning? What waste streams do
they produce and how are they
I treated? Are theyfriendly to the
environment and workers that use
them? The purpose of this fact sheet
is to help in determiningif these
cleaners can meet the needs and
expectations of your particular
requirements.

jPa__1 -1
L A N S I N G . MICHIGAN 48909
(517)335-1178'1"9218
FAX: (517)335-4729
SMALL BUSINESS CLEAN AIR ASSISTANCE

Reprinted with permissionfrom the Office of Waste Reduction Services, Environmental ServicesDivision,
Michigan Departmentsof Commerce and Natural Resources.
 E

FACT SHEET

IDENTIFY THE NEEDSOF YOUR
CLEANING SYSTEM
Switching cleaners is not as easy as it may
sound. There are many variables that affect
cleaning. Before evaluating alternative
cleaners, assess the cleaning process needs.A
check list of factors that affect the selection of soils, suchas lubricants and oils, which are
a cleaner and its method of application
follows.
What Types of Soil are to be
Removed?
The first step in assessing cleaning needs is to
identify the soils that need removal. The
composition of soils tobe removed is an
important variable in cleaner formulation. If
the manufacturing processand storage and
hvdling conditions of the part are known, the
type of soil that the part has been exposedto
can be predicted. For example,if the parts
have gone through machining operations,oils
and greases used for lubrication, cutting,
quenching and rust prevention must be
removed. Consider the removal of solder flux
residues when cleaning electronic
components. Parts exiting metal polishing andI
buffing operations are contaminated with
waxes and abrasives.
As can be seen in Table 1, there are a variety
of soils. Physical propertiesof soil include its
state (liquid or solid), viscosity, polarity and
meiting point. Solid particles (metal chips,
abrasive grains, pigments, carbon smut and
shop dirt) are usually held on the part by oils
and greases or static electricity. Becauseof
the large surface areaof the tiny particles, they
hold on to the part with great tenacity. Liquid
left on parts for a long timeor heated, can
polymerize toform tough hard films. Also,
soils with high viscosity and melting points
are generally more difficult to remove.
The polarityof soils will affect the typeof
cleaner selected. Polar or ionicsoils are
positively or negatively charged particles due
to the loss or gainof electrons. Most inorganic
soils (substances that are not compounds of
carbon) are polar, whereas most organicsoils
(substances that are compounds of carbon) are
non-polar. Water is a polar substance. Most
hydrocarbon liquids, with the exception of
alcohols, are non-polar. The importance of
polarity of both the soil and thecleaner will be
addressed later, in the discussion of the
cleaning mechanismof solvency.
Substrate
Zinc and aluminum alloys, because of their
sensitivity to alkaline cleaners--which are
corrosive-will require differentcleaners than
ferrous alloys. Aqueous cleaners for
nonferrous alloys willbe formulated with

TABLE 1

SMALL BUSINESS CLEAN AIR ASSISTANCE

. 2
 FACT SHEET
inhibitors that prevent the alkaliesfrom
attacking the sensitive metals. The inhibitors
deposit a thin protective layeron the metals
as soon as the contaminants are removed.
The majority of aqueous and semi-aqueous
cleaners are compatible with most metals and
plastics.
Part Size and Configuration
Part configuration, size, weight, porosity, and
quantity will not influence cleaner chemistry,
but will determine themethod of cleaning
and parts handling. Parts with rough
surfaces, overlappingjoints, blind holes and
tubing must be positioned to avoid corrosion
from thecany out of cleaner. Very large
castings may affect temperature of the
cleaning bath and more heat must be added to
the cleaning bathto maintain cleaning
efficiencies.
What is the Acceptable Level of
Cleanliness?
The levelof cleanliness is dependentupon
performance requirements of the part. Parts
going on to a paintingor electroplating
process will haveto be “cleaner” thanif the
parts were headed to a machining operation.
Many standard tests can be used to determine
if the acceptable levelof cleanliness is being
met. They range from visual inspection to
elaborate laboratory testing. A simple and
reliable procedureis the water-break test. A
surface is considered cleanif it can hold a
complete fdmof water on the surfaceof the
work after a 30 second drainage period. If a
water-break appears, the surfaceis not clean.
Other Considerations
Source Reduction: One wayof reducing
costs and increasing the potential of making a
successful conversionto a new cleaning
system is toreduce the amountof
contamination on the parts. Once the source
of the contaminants is identified,
modifications canbe made that will reduce or
SMALL BUSINESS CLEAN AIR ASSISTANCE
Y
Aiminate the need for cleaning.If the soils are:
i‘)received in raw materials, talk tosuppliersabout what
they can do to reduce the contamination;
)produced ingeneralmachiningoperations,minimize
the number of different coolants and/or lubricants
used;
lproduced in subassembly,findways to reduce
handling;or
lproduced during storage, reduce moisture.
?otential Impacts: In order to successfully
nake the switch to your new cleaning system
md reduce the impact to other operations,
:onsider the following questions:
What are the waste streams that will be
created by the new system and howare
they to be managed?
What new operating skillsor
equipment maintenance will be
needed? Process controlsfor aqueous
and semi-aqueous cleaningsystems
are greater than.those neededfor
solvent cleaningsystems.
How will the modification affect
product quality and operatingrates?
What are the capital and operating
costs? Energy requirementsfor
aqueous cleaning systemsare greater
than solvent vapor degreasing.
Andfinally, have any substitutions
been attempted in the past? What
worked? What did not work and why?
EVALUATION OF AQUEOUS AND SEMI-
AQUEOUS CLEANERS
Cleaning Step
linlike solvent cleaning, which occurs in one
;tep, aqueous and semi-aqueous cleaning
nvclves three steps: cleaning, rinsing and
wing. The cleaning phase in aqueous and
;emi-aqueous systems differ; however, the
insing and drying steps for aqueous and semi-
queous cleaning systemsare nearly identical.
3

C l e a n h ~Mechanisms
A discussion of aqueous and semi-
aqueous cleaning shouldnot
proceed without some
understanding of the followingfour
basic cleaning mechanisms:
Mechanical action - This is the
lifting of contaminants by physical
agitation, i.e., wiping, brushing,
spraying or abrading.
Chemical reaction - There are two
basic chemical reactions that can
occur in aqueous cleaning:
saponification and sequestration.
Saponification occurswhen the
alkalinity of the aqueous cleaner
“splits up” fatty acids,a
contaminant, to form water soluble
soaps that canbe easily removed.
Sequesteringagents
(polyphosphate salts of sodium) or
chelating agents (ethylenediamine
tetracetic acid) are added to cleaner
formulations to “tie-up” or
sequester the calcium and
magnesium ionsin hard waterso
that theydo not interfere with
cleaning. The hard waterions are
formed into ringed structures that
are water solubleand chemically
inactive. If not sequestered, the
ions will react with soap to form
scum.
Solvencv - Soils (or solutes) will
dissolve in a solvent forminga
uniformly dispersed mixture or
solution. Water, being a polar
substance, is the solventfor many
polar (or ionic) soils.
Hydrocarbons, being non-polar, are
the solvents for non-polar or
organic soils. Solubility is the term emulsifier. The nonpolar hydrocarbon tail ofthe detergent molecule
commonly used to describe the
ability of solids to dissolve in
SMALL BUSINESS CLEAN AIR ASSISTANCE
FACT SHEET
SURFACTANTS
Surfactants, also known as surface-active agents, are composedof
molecules that havetwo dissimilar parts resembling a tadpole. Thetail
end is made upof a chainof carbon atoms and is soluble in oil or, in
other words, attracted to dirt, oil and grease. The headis ionic and is
attracted to water. The nonpolar hydrocarbon end stays in the oil and
the polar, ionic endis in the water. Because of this antagonistic action,
surfactants like to concentrate at surfaces or interfaces.
As the number of carbon atoms included in the chains increase, the
surfactant molecules’oil attractive properties increase and their water
attractive properties diminish. Surfactants with relativelyhigh oil-
attractive properties are called emulsifiers. Emulsifiers coat oil and
grease, which formsan emulsion. The emulsifiers suspend the organic
soils and grease and other water immiscible soils in solution and prevent
redeposition. Surfactants with relatively low oil-attractive properties are
called wetting agents. Wetting agents increase the penetration of the
cleaner on the surface orsoil by reducing surface tension.Detergents
possess oil-attractive properties between those of wetting agents and
emulsifiers. Detergents lift soil from the surface of
the part by replacing
it with a surfactant, whiih has a greater affinity for
the soil.
Detergents or synthetic
surfactants
made
are
from
alcohols
petroleum
or
derivedfractions. Soap is an organicsurfactantformedby the reaction
of fatly acids(derivedfromnaturalfats,such as tallow, fish oil and
vegetableOils)andcausticsoda-
Illustration of M emuls$ed drop of oil in waterwith detergent as the
is in the oil,and theionic end is in the water.
4
 FACT SHEET

Because their performance can be affected

liquids and ihiscibility is the ability of a liquid by
to dissolve in another liquid. concentration, temperature and formulation,
aqueous cleaners can be usedin a variety of
Deteraencv - This is the lifting of soil froma
applications. Alkaline cleaners are formulated
surface by displacing it with surfactants that
to be either broad spectrum or precisely
have a greater affinity for the soil than the
applicable. Broad spectrum cleaners remove a
surface. The surfactants also provide for the
variety of soils while precisely applicable
dispersion of the contaminates, which is
cleaners are highly effective for a specific soil
necessary to prevent recontamination.
and not effective for many other soils.
Aaueous Cleaners
Composition
*How Do They Work?
Aqueous cleaners contain several chemical
Aqueous cleaners are categorized by pH level. components each having a distinct function
Cleaners with a low pH (2 to 6 ) are acidicand and effecton the way soil is removed.
those with a pHof 6 to 8.5 are considered
Alkaline Salts - Alkaline salts or alkalinity
neutral. Cleaners that have a high pH (8.5 to
builders are the major components in alkaline
13) are considered basicor alkaline. Acidic
cleaners contain excess hydrogen ions (H+) cleaners. They act as buffers that neutralize
acidic soils without excess loss of alkalinity
and alkaline cleaners contain excess hydroxide
and maintain the chemical environment in
ions (OH-). Acid cleaners are primarily used in
which other components of the cleaner operate.
re'moving oxidation scale and rust. Acid
cleaners contain mineral acids (nitric, Alkaline salts canbe categorized by the way
phosphoric, sulfuric, and hydrofluoric); they condition or soften water. The two groups
chromic acidor organic acids (acetic and of alkaline salts are precipitating and
oxalic); plus chelating agents, detergents and sequestering. Precipitating salts will combine
small amountsof water-miscible agents. with hard water minerals making them
insoluble. Sequestering salts will tie up
Aqueous cleaners, because they are water
minerals andsoils and hold themin
based, are most effective on polar, inorganic
suspension, making them soluble. Examples
based soils; however, a variety of additives
of some common cleanersare found in Table 2.
enhance the cleaners to provide for the removal
of organic soilsas well. In aqueous cleaning, a
combination of the cleaning mechanisms are
employed: mechanical action, chemical action
and detergency.
TABLE 2

I PRECIPITATING
TYPE I SEOUESTERING
TYPE I

1 Sodium metasilicate (PH12.5) 1 I

Footnote: Scislowski, Stan 'Cleaning Basics: Alkaline Cleaners" Metal Finishing.

 FACT SHEET

Sequestering type alkaline cleaners are more *Methods of Application

effective in preventing the buildup of hard
The cleaning phase inan aqueous cleaning
water scale on tanks and pumps. They are
system occurs in one step. The contaminants
effective in "peptizing" or holdingsoils in
are removed from the parts in the tank
suspension, which prevents them from
containing the cleaner. The parts leaving the
redepositing on the part. Phosphates are the
cleaning tank are coated with a wateddetergent
best overall builders, however, their discharge
film containing minor amounts of contaminants.
is subject to regulation.
Cleaning cycle times for aqueous cleaning in
Precipitating alkaline cleaners have higher industrial applications range from2 to 30
alkalinity and, therefore, higherpH. Silicates minutes.
are used in cleaning non-ferrous metals such The methodof cleaning is dependenton
as zinc, brass and aluminum because they production rates, available space, and size and
inhibit the corrosive action of the alkalinity.
shape of part. The basic cleaning methods are
One disadvantage in using the precipitating immersion (dipping or soaking) with or without
type cleaners is their poor rinsibility. Hard
agitation, spraying or by a combination of
water minerals that precipitate out cling to the immersion and spraying. The different types of
sides and bottom of the tank. This contributes
cleaning machines are found in Table3.
to the redepositionof soil onto the part.
Immersion - Immersion of parts into a cleaning
Surfactants - Surfactants can penetrate,
tank is simple, efficient and is the most widely
displace andor emulsify soil. (See Page 4).
practiced aqueous cleaning method. Tanks can
They are classified as anionic, cationicor non-
accommodate partsof unusual shape and are
ionic. Anionic and cationic surfactants are not costly toset up.
used in immersion cleaning. A non-ionic
surfactant shouldbe used if aqueous spray Installations may vary from single unheated
cleaning or agitation is used in order to tanks to multistage systems equipped with heat
minimize foaming. Some of the commonly and agitation. Aqueous cleaners needto be
used anionic surfactants are all@ benzene heated, especially when removing inks, waxes
sulfonates and naphthalene sulfonates. Most or solder pastes. The normal temperature of the
surfactants are biodegradable. Soaps (organic cleaner is in the range of 160"-200" F. The
surfactants) are destroyed in acid and perform speed of chemical reactions in cleaning doubles
better in alkaline conditions.The optimum with each 20" F rise in temperature. Heatis
alkalinity for soaps is 10.5. provided by steam coils, plate coils, direct firing
burners or immersion electric heaters. Low
Saponifiers - Saponifiers are alkaline cleaners temperature cleaners, which operate at a
that react chemically with insoluble animal temperature rangeof 70" - 120"F, are alittle
fats and vegetableoils to form water soluble more expensiveto purchase; however, they can
soaps. Saponifiedsoils float to the top of the greatly reduce energy costs and still provide
tank and are removed by skimming. Many good cleaning.
buffing compounds contain insoluble fats and
fatty acids. Workpieces and/or cleaning solution are
agitated to improve cleaning efficiency and
RustDroofinP Inhibitors - Compounds suchas reduce cycle times, temperature requirements
urea type inhibitors are added to the cleaners and the formationof air pockets. Agitation for
or used inthe final rinse water to protect the immersion cleaning includes workpiece
part from rusting. movement, suchas withdrawal and
reimmersion, pump agitation and ultrasonics.

SMALL BUSINESS CLEAN

AIR ASSISTANCE
6
 FACT SHEET

TABLE 3

MACHINE VOLUME OF PARTS TYPE OF PARTS I

I
flat bett
I
Medium-High Parts that drain easily
I
Rotary drum Medium-High
Small
I intricate parts
irregular
shapesthat
trap
and
fluids I
I
I
Turntable

Cabinet
positioning
special
II
requiring
Parts
Large sheets

draining
Medium to large sized parts
of anv shave
for

I
Pumps should be used for solution agitation
rather than blowersor compressors. Providing 1' I] Large flat partsare typically carried through
washer tunnels or monorail washers by
1

agitation through air pressure movement can

introduce contaminants into the cleaningbath
and can create excessive foaming. Ultrasonics
create cavitation (bubbles) at the cleaning
surface using high frequency vibrations.As
the bubbles form and collapse, they create a
of the,
scrubbing action that cleans the surfaces
part including blind holes andvery small
cracks and crevices.
Quite often, existing equipment suchas vapor
degreasers can be converted to the use of
I
1: :onveyor.
The spraying action providesa high levelof
.
1[mpactand agitation. Spray pattern, volume,
Ipressure and angle of spray can havean effect
3n cleaning efficiency. The higher the spray
Ipressure, the greater the mechanical cleaning
action. Spray pressure can vary from 2 to 2000
1
1psi. The design of the spray nozzleis critical
1because it provides the high impact, flat spray
1pattern and required flow rates.Increasing the
spraying pressure results in higher impact
1

aqueous cleaners. Under the directionof somc, . velocities and flow rateswith smaller drop
manufacturers of aqueous products, the sizes.
changes canbe implemented quite easily and While it is difficultto maintain the cleaner at a
economically. 1high temperature becauseof heat loss during
$Dray Cleaning - Spray cleaning involves the recirculation and spraying, itis still desirable
impingement of cleaning solutionupon the 1to keep the cleaner in the temperature range of
workpiece to remove soil. It is typically used 130"-160" F. Cleaners used in spray washers
for conveyorized part handling systems and require non-ionic surfactantsto prevent
high production rates. Spray washers consist oIf foaming.
a pumpto pressurize the solution, a reservoir Spray cleaning has some advantages over
tank, connecting piping, spray nozzles and a
immersion in that it takes less timeto clean
means for moving workpieces through.the and a lower concentrationof cleaner is used.
nozzles and cleaning solution. The amount of cleaner can be as low as 10% of
For small parts, cabinet or carousel machines that required for immersion cleaning. One
provide the simplest methodof spray cleaning I.
disadvantage, however, is that the capital costs
Inside the machines, a drum or worktable for spray cleaning is greater than for immersion
rotates or reciprocates so that surfacesof all cleaning.
the workpieces canbe exposed to the spray.

SMALL BUSINESS CLEAN AIR ASSISTANCE

7

Y
 FACT SHEET

*Safety- 1 in suspension indefinitely,and quick break

emulsions are temperature sensitive, which
Aqueous cleaners are nonflammable. Because
allows rapid separation of the water and organic
of their alkalinity, aqueous cleaners have an
contaminant.
ability to extractoils out of skin. Workers
should wear rubber gloves, aprons and face In cleaners containing quick break emulsions,
shields to prevent contact with skin. Handlingoils are put into suspension at operating
and safety requirements identified in the temperatures of 140" F and above. Upon
cleaner's Material Safety Data Sheet (MSDS) cooling to 85" F, the oil will separate from the
should be followed without exception. water and cleaning component mixture, forming
-Cost
two layers. The organic oil layer can be
disposed and thewaterkleaning component
Aqueous cleanersare available in layer can be reused. Cleaners with quick break
concentrated liquids and powders. Liquids emulsifiers cost more but have a longer life.
cost $6 to $10 per gallon when purchased in
In addition to choosing the right cleaner, there
drum quantities. In most applications, the
are various processes that can remove
cleaner is diluted with water within the
following range; 1 part cleaner to 3 parts contaminants so that the cleaner and rinse
waters can be can be continuously recirculated.
water (1:3) to 1 part cleaner to10 parts water
Free oils, emulsified oils, and suspended soils
(1: lo). In an effort to reduce waste disposal
costs, some manufacturersare packaging and metals are the contaminants that should be
liquid cleaners in recyclable 250 gallon
removed continuouslyor periodically from the
containers. aqueous cleaner bath and rinse water.
A continuous small stream of cleaner canbe
*Recoveryand Disposal
directed to a concentration or clarifier tank
Recovery - In parts cleaning systems, cleaning located adjacentto the cleaning bath tank (see
power and contamination level are inversely Figure 1 on page 9). The concentration tank
proportional: By continually removing provides for the separationof solids and liquids
contaminants from the cleaner, the cleaning by gravity and floatation. The free oils that
ability is maintained and thus the cleaner canfloat to the topof the tank can be removed by
be recycled indefinitely. oil skimming devicesor absorbent mats that
Increasing the longevityof the cleanerstarts pick up petroleum based fluids but repel water
with selecting the proper cleaner formulation. and product. The contaminants heavy enough to
Purchase acleaner that provides good settle out be passed through a bagfilter or
can
separation of the soils from the cleaner. New filter pressand removed as a sludge.
oil-displacing cleaners, or cleaners that are Microfiltration membranes, which have a pore
good detergents but poor emulsifiers, allow size of greater than0.2 microns, removedirt
the separationto occur. These cleaners will and contaminants (concentrate)from the cleaner
allow oilysoils and saponified soils to float to bath while allowing the cleaner and water
the surface where they can be skimmed off. (permeate) topass on through. The cleaner and
The heavy soils settle to the bottom where water are returned to the cleaning bathtank.
they can be filtered off and collectedas a Ultrafiltration membranes, which have a pore
sludge. size between 0.001 and 0.1 microns, canalso
Cleaners containing emulsifierscan form one remove contaminants from the rinse water.
of two types of emulsions: permanentor quick In addition to membrane technology, cold
breaking. Permanent emulsions keep theoil vaporization, ion exchange encapsulation and

SMALL BUSINESS CLEAN AIR ASSISTANCE

8

c
 FACT SHEET

chemical treatment systemscan be used to Considerations” sectionof this fact sheet for
purify cleaners and rinses so that they can be more details.
reused.
Even though the cost of equipment to recover
Disposal - When it comes to disposing a and treat aqueous cleaners can
be expensive,
cleaner bath, there are a few options: the same equipment could be used on other
waste streams generated at your business such
*discharge to a holding tank from which the waste is
subsequentlypumpedandhauledbyalicensed
as machining coolants and mop water.
hauler for appropriate disposal at anfacility;
approvedSemi-Aqueous Cleaners
*discharge to surfacewatersorgroundwater if *How do They Work?
permitted or exempted by the Michigan Department
Semi-aqueous cleaners, also known as
of Natural Resources (MDNR) under the Michigan
emulsion cleaners, are nonchlorinated
Water Resources Commission Act (Act245 of 1929);
hydrocarbons dispersed in water with or
or
without the aidof emulsifiers. They, therefore,
*discharge to a Publicly-Owned Treatment Works have the cleaning properties of solvency and
(POTW) with the approvalof the POTW. detergency.
Approval for discharging to POTW,
a surface Whereas the cleaning phase for aqueous
water or groundwater may be contingent upon cleaners occurs in one step, the cleaning phase
pretreating the waste to remove the oils and for semi-aqueous cleaners generally occurs in
grease and adjusting the
pH and removing two steps. The soil and contaminants are
organic matter and dissolved metals. Referto dissolved in the primary tank containing the
the “Environmental Regulatory cleaner. In the secondary tank, the soiVcleaner

FIGURE 1.

Recovery / Recycling of Cleaner Bath& Rinse Water

2 STAGE PARTS WASHER WQ n L I I * T D *

EMULSIFIED

SUSPENDED
SOLIDS
I PROCESS!
TANK

TRACE OROANICS
DISSOLMDSOLIDS
METALS

b
CONCENTRATE
POST TREATMENT OR DISPOSAL

MICROFILTRATION
ynatec
systems
OR

SMALL BUSINESS CLEAN AIR ASSISTANCE

9
 mixture is rinsed off the part with water. Like ,Methods of Application
aqueous cleaning, the partsthen proceed Immersion is the most common method of
through the rinsing and drying phases. :ontacting the part with the semi-aqueous
Due to their solvency properties, semi- :leaner. Because of the relatively low flash
aqueous cleaners are effective in removing Ioint of organic solvents, terpenes in particular,
heavy greases and waxes.They traditionally :here are limitationsto the degreeof heating and
have been usedas an in-process cleaner, gitation applied to the cleaning tank.
removing the bulkof the soilsso that further To avoid ignitionof solvent vapors, it is
manufacturing can be conducted without :ecommended that a minimum of 30" F is
difficulty. naintained between the operating temperature
*Composition 3f the cleaner and its flash point. Terpenes,
which have a flash point in the range of 115" to
There are two basic components of semi- 120" F, should not be heated above90" F unless
aqueous cleaners,and they are categorizedby jiluted with water. Glycol ethers and NMP
their ability tomix with water. Water have flash pointsof 142" and 204"F,
immiscible components include: respectively.
Terpenes - These are natural hydrocarbons Although agitation increases cleaning efficiency
derived from plants. d-Limonene is extracted and emulsion stability, care must be taken to
from the rindsof lemons and oranges. Pinene avoid creating mistsof concentrated semi-
is extracted from the bark
of pine trees. aqueous cleaners. These mists can be ignited at
Esters - Aliphatic monobasic esters and room temperature.
dibasic esters are usedin semi-aqueous .Safety
cleaners.
In addition to the flammability concerns
Water miscible componentsof semi-aqueous identified above, there are some worker safety
cleaners include: concerns associated with terpene cleaners.
Glvcol ethers - There are two common kinds Since theyare derived from plants, they can
of glycol ethers: e and p series. The p-series have an odor that is bothersome to some
are typically used in cleaning formulations workers. Ventilation systems may have to be
because theyare safe for personal contact and provided in areas where the cleaners are used.
not regulated under Section 3 13 of the Toxicity studies on terpenesas well as other
Emergency Planning and Community Right- cleaner componentsare being conducted.
to-Know Act. According to an EPA report entitled Aaueous
Ketones - Commonly used ketones in cleaning and Temne Cleaning Interim ReDort, ... "

are acetone and methyl ethyl ketone. aqueous and terpene cleaners canbe used in a
manner safeto workers, consumers,and the
Alcohols - Commonly used alcohols used in
general population given appropriate
cleaning are ethanol and isopropyl alcohol. technological changes and exposure control
Amines - N-methyl-2-pyrrolidone (NMP) is practices."
as a
an amine that is used in paint strippers Since the cleanersare moderate skin irritants,
replacement for methylene chloride. solvent resistant gloves and aprons andeye
Surfactants - See Page 4 for definition. protection shouldbe worn where exposureis
likely. Handling and safety requirements
Alkaline Builders - See Page 6 for definition.
I identified in the cleaner's Material Safety Data

I SMALL BUSINESS CLEAN AIR ASSISTANCE

10
 FACT SHEET
Sheet (MSDS) should be followed without counterflow system, water in thefinal or
exception. secondary rinse tank is used to replenish the
initial or primary rinse tank.
*Cost
Heat, agitation and chemical additions will
Terpenes, esters and glycol ethers are priced at
increase the effectivenessof rinsing. Rinse
$10 to $18 per gallon when purchased in drum
water should be warm as opposed to hot or
quantities. NMP's cost is $25 to $30 per
gallon. cold. Hot water may set some of the residues
on the part orform oxide films. Temperature
-Recovery and Disposal also affects the surface tensionof water. More
Recovev - Since oils tend to dissolve in semi- droplets will cling to parts rinsed with cold
aqueous cleaners, skimmers and coalescers arewater than with warm water. Ultrasonics or
not as effective in the removalof these pumps provide the mechanical action
contaminants. Concentrated semi-aqueous necessary to increase rinsing efficiency.
cleaner bathsare not reclaimable. Consideration should be given to using
Contaminants dissolve and become locked up deionized water for rinsing parts, which
in the hydrocarbon solvent making separation eliminates the spotting causedby the salts
of the dirt from the cleaner difficult. Once they found in hard water. Adding isopropyl alcohol
become contaminated, the cleaning bath must to the rinse water improves rinsing by reducing
be disposed. The rinse watersof the semi- the surface tensionof the water.
aqueous cleaning system canbe recycled by Drying Step
microfiltration membranesor ion exchange. Unlike solvent vapor degreasing, in which
Disposal - The disposal options €or semi- parts come out dry, aqueous and semi-aqueous
aqueous cleaning baths diluted with water arecleaned parts are wet. Drying canbe
the sameas those identified for aqueous accomplished by a variety of methods
cleaning baths. Concentrated semi-aqueous depending upon part configuration and the
cleaners, becauseof their highBTU value, may speed required. Typical methods of drying
be picked up by a licensed hauler and taken to include evaporation, mechanical displacement
approved facilities that process wastes into a of water or displacement using another fluid.
fuel thatis burned for energy recovery. Evaporation under ambient conditions is slow
and can leadto rusting. Evaporation is
Rinsing Step
accelerated by putting the parts in a chamber
To obtain the required level of cleanliness,
Air knives blow off
that circulates heated air.
parts exiting the aqueous or semi-aqueous
water from the part with compressed air.It
cleaning bath shouldbe rinsed. Rinsing is
minimizes the deposition of dissolved solids
necessary to remove the residual layer of
that may remain on the part. Centrifugal
contaminants and cleaner. Not all cleaners
drying spins water off. Special protectiveoils
rinse the same. Semi-aqueous cleaner residue
displace water from the part and replaceit with
is more difficultto remove than aqueous
a film that prevents corrosion.
cleaners. The level of rinsing ranges from
simple immersion or spray using tap water to ENVIRONMENTAL REGULATORY
multiple rinse tanks using deionized water. CONSIDERATIONS
Waste streams generated from aqueous and
To minimize water usage, a countefflow
semi-aqueous parts cleaning systems can
rinsing system shouldbe used. a two tank
'In

include usedoils, wastewater (cleaning baths

and rinse waters) and even some small

SMALL BUSINESS CLEAN AIR ASSISTANCE

11
 FACT SHEET

amounts of volatile organic compounds ,Keep storage tanks and containers

(VOCs). In general, the options for
wastewater disposal are: (1) contracting with
a hauler to deliver it toa commercial
treatment and disposal facility, or(2)
pretreating the wastewater on-site prior to
discharge toa POTW or other approved
receiver. On-site pretreatment may generate
sludge, which is another waste stream
requiring disposal. The environmental
of these waste
regulatory considerations for all
streams are discussed below.
Used Oils
Used oils that are separated from cleaner
solutions by devices suchas skimmers and
coalescers can be disposedin the same
manner as other used oils that may be
gexierated from other production or
maintenance processes. If the used oil is
recycled, the generatoris exempt from the
requirements of Michigan’s Hazardous Waste
Management Act, 1979 PA 64, as amended
(Act 64).
If the used oil will
be burned for energy
recovery, the generator will be subject to
hazardous wasterequirementsunder Act 64.
Used oil destined for burningis identified as
either on-specification or off-specification.
Used oil is considered tobe “off-sped’unless
laboratory results orother documentation
shows that contaminant levels do not exceed
specifications. For more information
regarding the requirementsfor this
management option, contact your nearest
Michigan Departmentof Natural Resources’
(MDNR) district office.
All generators of used oil must comply with requirements pursuant to state and federal
the managementstandards promulgated under hazardous waste regulations. This would
special authorityof the federal Resource
Conservation and Recovery Act @CRA),
Section 3014(a). These standards were issued disposal facility(TSDF).
to control potential risks from recycled used
oil and, accordingto these requirements, a
generator must:
in good condition;
,Label storage tanks, “used oil”;
Clean up any used-oil spills orleaks to the environment;
and
Use atransporterwithanEPAidentification (ID)
numberwhenshippingused oil off-site. The
transportationof usedoil in Michiganis also subject to
the requirements of Michigan’s Liquid Industrial Act,
1969 PA 136asamended (Act136). Acontract hauler
of liquid industrial waste, regardless of whether or not
the material is hazardous, must be licensed and a
manifest must accompany the shipment.
Wastewater (Offsite Treatment &
Disposal)
Before sending spent cleaners (or liquid
industrial waste) toan off-site facility for
treatment and disposal, it is the generator’s
responsibility to determine if the wastea is
hazardous waste. There are two categories of
hazardous wastes: listed and characteristic.
Listed wastes are waste materials listed by
name in either Act 64 or the Resource
Conservation and Recovery Act (RCRA).
theCharacteristic wastes are wastes that possess
any of the characteristics identified in state
and
federal hazardous waste law. These
characteristics include corrosivity, ignitability
,
reactivity, toxicity and severe toxicity.
If the wastewater is determined to be non-
hazardous, it is not regulated under Act64 or
RCRA. However, like used oil, the
transportation of the wastewater is subject to
Act 136.
If the liquid industrial waste is determinedto be
a hazardous waste, itis subject to all applicable
include transporter licensing and disposal aat
licensed hazardous waste treatment, storage or

SMALL BUSINESS CLEAN AIR ASSISTANCE

12
 FACT SHEET

Depending on the hazardous waste Federal Regulations (40 CFR Part 403). These
characterization and amountof recoverable standards are designed to prevent pass through
go
oils, liquid industrial wastes will typically or interference with the treatment processes at
to one of three types of facilities. the POTW. Categorical pretreatment standards
regulate the levelof pollutants discharged to
Used oil processors will treat non-hazardous
the POTW for specific typesof industries. The
liquid industrial waste containing recoverable
categorical pretreatment standards appear 40 in
oils in additionto processing used oils. The
CFR Parts 405 through 47 1.
used oils are separated from the wastewater
and are processed for fuel use or non-fuel pH Adiustment - Since aqueous cleaners are
industrial uses, suchas cutting and honing oils. alkaline and have a pH ranging between 7 to
The treated wastewater is discharged to a 12, pH adjustment may be required prior
to
POW. i !sanitary discharge. Sulfuric or hydrochloric
acid are typically used to lower the pH.
Licensed hazardous waste TSDF facilities will
process both non-hazardous and hazardous Biodearadable
- - Many manufacturers claim
liquid industrial wastes containing recoverable their aqueous and semi-aqueous cleaners are
oils. The used oils are reclaimed and the biodegradable. This canbe somewhat
treated wastewater is discharged to a POTW.misleading because the term biodegradable
A price break is givento non-hazardous liquid applies onlyto the cleaner. It does not applyto
industrial wastes. the contaminants in the cleaner. Also, some
surfactants take too longto break down into
Licensed hazardous waste TSDF facilities will
the constituent elements to be environmentally
solidify both non-hazardous and hazardous
acceptable. If the amount of dissolved metals
liquid industrial wastes. The solidified
and/or emulsified oils in the waste stream
material is landfilled. This disposal option is
exceeds thePOTW, NPDES or groundwater
best suited for wastes that are heavily
permit discharge limits, they will have to be
contaminated and/or have very little BTU
removed from the waste stream prior to
value.
discharge.
Wastewater (On-site Pretreatment) Free Oil Removal - Free oils will rise quickly
Businesses must sometimes pre-treat chemical to the surface of a nonagitated tank. Skimmers
wastes priorto disposal. The level of have either a rope or drum that liftsoilthe
pretreatment depends upon the quantity and from the surfaceof the cleaner and deposits it
nature of the contaminantsand the limitations into a holding tank. Devices such as
imposed by the POTW if discharged to a coalescers and centrifuges will improve the
sanitary sewer; the National Pollutant separation of free oil from the cleaner.
Discharge Elimination System (NPDES)
permit if dischargedto surface waters; or state EmulsifiedOil and Metal Removal- Removing
groundwater permitif discharged to the dissolved metals and emulsified oils from
groundwater. aqueous cleaners canbe achieved through
chemical treatmentor membrane separation.
There are twotypes of national pretreatment The chemical removalof stable oil-water
standards that control pollutants introduced emulsions and dissolved metals occurs in three
into a POTW: prohibited discharge standards steps:
and categorical pretreatment standards.
Prohibitive discharge standards are contained (1) a coagulant is addedto break the oil-water
in the general pretreatment regulations, which emulsion and a hydroxide, such as lime,
are found inTitle 40, Part 403 of the Code of precipitates out the dissolved metals;

SMALL BUSINESS CLEAN AIR ASSISTANCE

13
 FACT SHEET
(2) a flocculent is added to agglomerate the for acid solutions.”
tiny oil particlesand metal precipitate into
Rule 285(o)(iv), “the permit system does not
particles; and
apply to ...equipment used for... cleaning ... if
(3) the particles are separated from the clean the process emissions are only released into the
water through sedimentation and removed. general in-plant environment.”
The chemical treatmentof wastewater
Undiluted Semi-AaueousCleaners - Semi-
generates sludge, which is typically dewatered
aqueous cleaners used in concentrated form
prior to disposal.
could meet the permit exemption identified in
Reverse osmosis can remove dissolved metal Rule 285(o)(iv).
ions from the cleaner solution. Ultrafiltration
Although aqueous and certain semi-aqueous
membranes can remove emulsified oils.
cleaning systems are exempt from permitting
Sludge Removal - Pretreatment of wastewater requirements, all cleaners are still subject to
may result in creationof a sludge. The sludge Parts 6 and 7 of the Act 348 rules, which
must be evaluated to determine if it is regulate the usageof VOCs in existing andnew
sufficiently dewatered and if it is a hazardous cold cleaners, respectively. The rule requires
waste. If the sludge hasbeen determined to that the equipment meet various design criteria
be ion-hazardous waste, it canbe disposed in and good operating practicesto minimize the
a sanitary landfill licensed under Michigan’srelease of VOCs.
Solid Waste Management Act,1978 P.A. 6 4 1 ,
For moreinformation concerning:
as amended (Act 641). Liquid waste cannot
be landfilled. *The disposal of solid and hazardous wastes and the
transportation of liquid industrial wastes, contact the
Air Contaminants
WasteManagementDivisioninyourlocal MDNR
Michigan’s Air Pollution Act,1965 P.A. 348, district off ice.
as amended (Act348) regulates sourcesof air
pollution. According to Rule 201, ... a
“ *The NPDES requirements, contacttheSurfaceWaster
person shall not install ...equipment...which Quality Division in your local
MDNR district office.
may emit an air contaminant unless a permit .Discharges to sanitary sewers, contact yourP O W .
to install...is issued.”
*The regulation of air contaminants, contact the Air
Aaueous and Diluted Semi-Aaueous Quality Division in your local
MDNR district office.
Cleaners - Parts washing processes utilizing
aqueous cleaners and semi-aqueous cleaners *Suppliers of semi-aqueous cleaners and aqueous
one or all of the parts washing equipment, contact the Environmental
diluted with water could meet
following permit exemptions. Services Division, Departments of Commerce and
Natural Resources.
Rule 281 (d), “the permit system does not
apply ...to equipment usedfor washing or Michigan Departmentof Natural Resources
Environmental Protection District
Offices
drying materials, wherethe material itself
Marquette ....................... ..(906) 228-6561
cannot become anair contaminant, if no Cadillac ...................... ......(616) 775-9728
volatile organic compounds are used in the Gaylord ................... ..........(517)732-3541
process and no fuel is burned.” Grayling .................... ........(517) 348-6371
Bay City .................. ..........(517) 684-9141
Rule 285(i)(iii), “the permit system does not Grand Rapids ......... ...........(616) 456-5071
apply to ... equipment for surface preparation Shiawassee .............. .........(517) 625-4600
of metals by use of aqueous solutions, except
Plainwell ................. .........(616) 685-9886
Jackson .................. ...........(517) 780-7900
Livonia ................. ............(313) 953-0241
SMALL BUSINESS CLEAN AIR ASSISTANCE
14
 FACT SHEET

REFERENCES
Chiarella, William J., "Alternative Chemicals and Processes
in Metal Cleaning,"Metal
Finishinq, Vol. 88, No. 12, Dec. 1990, pp.21-23.
Environmental Restoration and Waste ManagementUS. and
Air the
Force Engineering
and Services Center,Solvent Substitution,
[A Compendium of Papers FromThe First
Annual International Workshop on Solvent Substitution], Phoenix: USDOE, December
1990, DE-AC07-761D01570.
.Huddle, Richard F., "Fact Finding First -
How to Plan the Best Possible Parts-
Cleaning System," Products Finishing, March 1990, pp.70-75.
*Innes, William P., "Metal Cleaning,"Metal Finishina-
Guidebookand Directorv Issue,
-
'90, Vol. 88, No. A,
1 Mid-January, 1990, pp.106-124.
OJansen, George and Jan Tervoort, "New Concept for Alkaline Cleaning -- Low
Temperatures and Infinite Bath Life," Metal Finishing, April 1985, pp.63-67.
. *Mohler, J. B., "Alkaline Cleaning for Electroplating," Metal Finishinq, Sept. 1984,
pp.49-52.
=Obtzut,John J., "Metal Cleaning: The Key Element
to Better Finishes," Iron Aae, 7
June 1982, pp.57-62.
-Overton, Cecil, "Cleaning With Kindness,"Products Finishing. April 1992, pp.98-102.
*Polhamus, Robert L., "Precision Cleaning of Metal Parts Without Solvents," Metal
Finishing, September 1991, pp.45-47.
*Quitmeyer, Joann, "NewTechnology Alkaline Cleaners Replace Chlorinated Solvent
Degreasers," Lubrication Enaineering, March 1991.
*Scislowski, Stan, "Cleaning Basics: I Part--
Introduction,"Metal Finishing,
Vol. 88, No.
1, Jan. 1990, p.33.
-
II Soils," Metal Finishinq,Vol. 88, No. 2,
*Scislowski, Stan, "Cleaning Basics: Part
Feb. 1990, pp.43-46.
*Scislowski, Stan, 'Cleaning Basics: Synthetic Detergent and Cleaner Selection,"
Metal Finishing,Vol. 88, No. 3, March 1990, pp.51-52.
Vol. 88, No.
~Scislowski,Stan, "Cleaning Basics: Alkaline Cleaners,"Metal Finishing,
4, April 1990, pp.23-25.
*Scislowski, Stan, 'Cleaning Basics: Emulsion and Solvent Cleaners,"Metal Finishing
Handbook, Vol. 88, No. 5, May-1990, p.63.
Yo& Reinhold Publishing Cop., 1963.
*Spring, Samuel, Metal Cleaning, New
*Temple, StephenD., "A New Era for Aqueous Cleaning," Products Finishing, March
1990, pp.76-83.

SMALL BUSINESS CLEAN AIR ASSISTANCE

15
 FACT SHEET

REFERENCES (continued)
*“Terpene Solvents Prevent Ozone Risk,” American Machinist, Jan.l989,pp.25-27.
--
=Tool and Manufacturina Enaineers Handbook. Vol 3 Materials. Finishina and
-q, Ed. by Charles Weck and RaymondF. Veilleux. Dearborn, MI: Society of
Manufacturing Engineers, 1985.
United States Environmental Protection Agency,ICOLPTechnicalCommittee.
Alternatives For CFC-113 and Methvl Chloroform in Metal Cleaning,
USEPA, June
1991, EPN400-1-91-019.
=UnitedStatesEnvironmentalProtection Agency,ICLOP TechnicalCommittee.
Eliminatina CFC-113 And Methvl Chloroform in Precision Cleanina ODerations,
USEPA, June 1991, EPN400/1-911018.
*UnitedStatesEnvironmentalProtection Agency,GuidetoCleanTechnoloav:
Alternatives to Chlorinated Solvents For Cleanina And Deareasing, USEPA, July
1992.
*United Stated Environmental Protection
Agency,Guide toCleanTechnoloav: Cleaning
and Deareasina Process Chanaes, USEPA, May 12,1992.
Agency, Officeof Toxic Substances.Aaueous
*United States Environmental Protection
and T e m n e Cleanina InterimReDOIt, Washington, D.C.: USEPA, November 15,
1990.

For more information on waste reduction for

businesses and the Small Business Clean Air
Assistance Program, contact the:
EnvironmentalServices Division
Michigan Departments of Commerce and
Natural Resources
P.O.Box 30004
Lansing, Michigan 48909
(517) 335-1 178
Toll Free:
1-8oO-NO-2-WASTE

SMALL BUSINESS CLEAN AIR ASSISTANCE

76

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 State of Ohio
Environmental Protection Agency Fact Sheet
" Prevention
Pollution

Extending the Lifeof Aqueous

Number 31
September 1995
~-
CleaningSolutions

The bath lifeofan aqueous cleaning solution is limited by the buildup of the contaminants
removed from parts. Although the cleaners may avoid some.ofthe environmental issues
of the bath to maintain
associated with cleaning with organic solvents, the periodic disposal
its own environmental and economic problems. These problems can
part quality results in
be minimized through techniques to extend the life
of and recycle aqueous cleaning baths.

Don't TradeOne
Problem for
Anothe'r
In recent years, a number of
companies have switched
from cleaning using cldori-
nated solvents, suchas 1,1,1-
trichloroetllane or trichloro-
ethylene. to cleaning using
aqueous solutions. These
cleanersare water-based
solutions that CUI contain a
nwnber of chenuc;ll compo-
ncnts such as dctergents.
surfactants. saponifiers and
rustproofing inhibitors. They
are hTically used i n Inulti-
stage systenls. which may
involve immersion. sprays,
ultrxsonics. rinsing. drying or
other steps.
Two of the key motivators for
finding alternatives to
solvent-based cleaning are
avoiding or minimizing the
a i r emissions andluz~rdous
waste generation associated
with these processes.
However. a company that
switches to an aqueous
cleaner may find itself\\ih a
new problem in a new
enviro1mentdmedia. Both
the components ofthe
cleaner and the contanunant
(typically oilsand greases)
'.*&e now introduced into the
wastewater.
Fortunately, the impact of
aqueous cleaning on waste-
water can be minimized.
Elqending aqueouscleaning
bath life through operating
changes andor tluough
recycling m y offer an
environmentally sound
dtenutive. It may also
reduce costs,allouing
Cl~31UIlg SOlUtiOllSIO bc
reused repealcdly. instead of
becoming simply a wasted
valuable raw n~aterial.
Companies that are cllrrently
in tlle process ofselecting a
new aqueouscleaning system
may want to consider
recycling options earlyi n the
selection process. Tllis will
help them select proper
cleaning equipment and a
cleaning solution that both
effectively cleans parts and
can be recycled in the most
cost effectivc manner.
The Problem of
Contaminants
The life of a cleaning bath
will be limitedby the build
up of contaminants as they
are removed from the parts.
With time and use,cleaning
effectiveness will be reduced
(Lindsey et all. 1991).
There are many options for
nlaintaining cleaning baths
and estending their lives.
The option that] d l be most
efTective and feasiblewill be
determined by a number of
factors. including the volume
and nunlberof the baths. and
tlle contaminant or contami-
~lantsmost responsible for
degrading thequdity of the
bath. Tlus c m include non-
emulsified oil, emulsified oil,
ions suchas sodium or
chloride. suspended solids
and dissolved solids.
One ofIhe most significant
factors is whetller tlle oil is
emulsified, and howit
became emulsified. Oil can
bccolne emulsified by a
variety offklors n~ch as
heat, agitation orthe
chemica? components ofthe
aqueous bath. Some options
only address non-emulsified
oil, some can also remove oil
that is mechanically emulsi-
fied,and some can even
remove chemically emulsi-
fied oil.
Mechanically ernulslfied oils
are oils that have been broken
apart by physical forces, such
as agitation or heat. during
cleaning operations. Over a
period of time, if these
physical forces are removed.
thcse oils may separate out by
themselves. nus process c<m
be accelerated by equipment
such as coalescers or
separators. discussed laterin
this fact sheet.
More soplusticated recycling
equipment can remove even
cllemically emulsified oil.
This is oil wluch has been
suspended by components of
the cleaner. wlucll were
specifically designed to
emulsify and suspendtlis oil
to avoid redeposition
(F'cterson. 1995). Quipment
to remove these oils is
typically the nlost capital
intensive ofthe systems
discussed in t h i s fact sheet.

Printed on recycled and

8 recyclable paper Office of Pollution Prevention, Ohio Environmental Protection Agency, P.O. Box 1049,
Columbus, OH 43216-1049, (614) 644-3469
Pollution Prevention
Extending the Life of Aqueous Cleaning Solutions
Because of the problems
inherent
to
removing
chemically emulsified oil, the
chemical make-up ofthe
cleaning bath used will
partially determine which
systems are necessary to
adequately remove the oil.
A cleaning solution which
has less power tochenucally
emdslfy the oil will inher-
ently have lesscleaning
ability. Increasing the ability
of the Eleaner to remove oil
results in a trade-off of
decreasing ability ofthe oils
to be easilyseparated from
the cle'aner at a later point in
time for recycling purposes
(Durkee. 1991).
Extending Bath
Life Prior to
Recycling
Some options doesist for
estending the life of an
aqueous cleaning bath
without the purchase of
additional equipment such as
recycling systelns. These
options are discussed below.
Reduce sourcesof
contamination Some-
contaminants. such as metal-
working fluids or finger-
prints. can be reduced at the
source through operating
changes or increased care i n
lmndling during the pro-
cesses prior to the cleaning
stage. Some material, such
as a rust protectant which a
supplier intentionally puts on
"
2
a nletal p a n becomes a
. contaminant at a later point
(and has to be removed. The
company performing the
cleaning should carefully
consider its inventory
practices to determine if any
of this contamination can be
avoided or minimized.
Reduce heat and
turbulence during off-
-
hours Reducing the heat
'ind turbulence in aqueous
baths during the night or off-
hotus may result in more of
the mechanically emulsified
oil rising to the top of the to determinethe combined
bath. Thus will allow more of
the oil to be skimmed in the
monung before operations
begin.
Partial bath replenish-
ment - A company may be
able to estend>ath life by
only partially dumping baths chenucally or mecha~ucally
and adding fresh water and enlrdsified oil. non-emulsi-
chemicals to bring lllc
solution up to volume. This
nlay increase the effective-
ness of thecleaning bath
sufficiently for continued
cleaning. Evenhally,
however. chemicalswill need
to be added at a rate that
results in costs greater than
the savings from dumping
the bath and nusing a new
solution. This indicates tllat cstend bath life. Filters can
the entire bath should be
dumped and refillcd (PRC
En\irorunental. 1989).
Recycling filtering an electrocleaner
and acid pickle (1 05 gallons
each). They estimlted that
Marly different typesof
the filtration exqended the life
systems exist toseparate oil
of the electrocleanerby 10
and other contamination
times.
from the aqueous cleaning
baths. During discussions
The results of a user survey
with equipment vendorsit is
in the book, "Pollution
important to emphasizethe
Prevention and Control
follouing: the company's
Technologies for Plating
intention to reuse the aqueous
Operations" indicatedthat of
batla, not simply pretreat
them before disclmrging: the 265 alkaline soak processes.
21 utilized in-tank filtration
temperature ofthe baths; and
and oneused exTernal
the pH of the baths.
filtration for bath mainte-
nance (Cushnie, 1994).
The company willalso need
However, some experts
volume ofthe cleaning tanks
indicate that the cleaning
and the average time between
ability offilters is insufficient
tank changeout. and should
to make a significant ch<ange
prepare copies of material
safety data sheets. It should in bath life because of their
inability to remove any
also consider analytical
emulsified oil. One vendor
testing to detennine whether
the pri~naqcontalnination is indicated that filters may
become coated so quickly
with oil tllat the cost ofeither
ficd oil. suspended solids. replacing or washing the
dissolved solids. or other type filters might outweigh the
of contaminant. Some financial benefits of cxtended
vendors will conduct this bath life.
testing themselves.
Esperimentation with filters
may indicate whether or not
Filtration
they significantlyincrease
Literature indicates that in-
bath life for a particular
application.
tank filter cartridges can
Mechanical
be selected to remove non-
separation of oil
cmulsificd oils or solids, but
not crnulsificd oils.
Several different types of
equipment existto separate
One company reported the
certain oils from Lhc cleaning
purcllase of used filtration
solutions.
eqipmenr for $500 uith
installatien costs of $350 for

Decantation fig11 -
volumes ofnon-soluble oil
(only) can be removed
through decantation ofthe
oily cleaning solution while
in a holding tank. These
systems should be designed
to prevent oil from being
circulated through process
pumps, so the pumps can not
further emulslfy the oil.
Collected oil ~ r be
n skimmed
into a decanting chamber
where a more complete
separation tan be achieved.
(Temple, 1990).
-
Separation Both non-
emulsified oil and mechani-
cally-emulsified oil (but not
chemically emulsified oil)
can be rexnoved through a
separation unit (tlus may be
referred to as a plate separa-
tor, a gravity separatoror a
coalescing unit)or a combi-
nation of filtration anda
separation unit. Scparation
units can be central or
dedicated. and ccm takc up
relatively small amounts of
space.
These units speed up the
natural sepalration of me-
chanically emrdslfied oilby
agglomerating oil droplets.
This muses them to separate
from the cleaner dueto
differences in density
(Peterson. 1995).
Although the varietyof
separation units availablc
filnction in essentially the
same nunner. they will differ
greatly from eachother based
I oil layer
U
I
coalescing media or separation plates
.... Figure I : Scpurutor
on the vendor andon the
specific needs ofthe cus-
tomer. See Figure 1 for an
esanlple of a generic
separation unit.
One advantagc of conlbina-
tion filtratiodseparation
systems is tlmt they do not
risk rcmo\ing the additivcs
in the aqucoos bath. as
mcnlbranes frltration q'stenls
somctimcs do.
ow clcctrical c0111ponc11t
manufacturer suitchcd from
simple manun1 skimnung to a
separation system. The
vendor analyzed a sample of
the used bath to deternune
the internal configuration of
the coalescing unit. The
system was installed for less
tllan $10.000 and rcsultcd i n
a first year sl\ings of more
than $29.000 chemical costs
(Batutis. 19S9).
Membrane Technologies
In traditional filtration. the
entire stream is passed
throogh a filter. Crossflo\\-
\-
oil outlet
filtration. typically uscd for
ultr,fllltration and
nucrofiltration, flows the
stream acrossa menlbranc
using pressure toforce
filtration to occur. See
Figure 2 fora diagram of
crossflowfiltration.Ultr,aIil-
tration and nucrofiltration
nuy offcr effective nleans to
renlove contaminants and
increase bath life. They may
also bc the most capital
intensive options discusscdi n
this fact shcct. The type of
membranc system choscn
depcnds 011 fictors such a s
Ihe most significant type of
contanunation,tllc volumeof
fluid to be processed. and the
teIllperahIre ofthe solution.
Suspended solids may nced
to be removed priorto
ultrafiltration. which is
capable of rcnloving dis-
solved .solids and/or
mechanically or chemically
emulsifiedoil. It removes
particles in the 0.00j - 0.1
micron range.
- works best nith non-silicated
Fact Sheet
Many membranesare not
compatible with hot andor
caustic solutions. This may.
preclude use of these systems
entirely, or necessitate the use
of a holding or cooling tanks,
which would require e x m
floor space. Ultrafiltration
may require some type of
pretreatment, either by
filtration or by oil separation.
For instance. a vendor may
provide packages with
attached filtration for
suspended solids. O r , the
system may usea tramp oil
separator for pretreatment to
remove mechanically
dispersed and freeoils.
Which system is best can
only be determined after
testing and through conunu-
nication with vendors.
Microfiltration remo\.es
particles in range of0.1 to 5
nucrons. Many
nlicrofiltration systems are
a\.ailablc ~\-ithceramic filtcrs
that can \vithstand the high
ternpcntures and caustic
solutions associated uith
many cleaning baths. This
may avoid the need for a
holdmg tank or cooling tank.
saving floor space. A
nucrofiltration unit may take
up less space than anofice
dcsk.
Microfiltration a 1 1 remove
solids, non-emulsificd oil, or
mechanically or chemicidly
emulsified oil. but ma!.
require pre-filtration or pre-
separation. Microfiltration
cleaners.
3
 E

Pollution Prevention
Extending the Life of Aqueous Cleaning Solutions

The book “Pollution Pre\.en-
tion and Control Teclu1ology
for Plating Operations”
provides an example of
return on investmentfor a
microfiltration system. The
bath volume was 2400
gallons, and the cleaner cost
was $0.42/gallon. J2quip
ment and installation costs
were $27,000, and operating
costs were $6,25O/yearu. Total
savings were$18,7 15. The
return on investment was 2.1
years (Cushnie, 1993).
One of the mostsignificant
concerns regarding the use of some issues associated with pany resolved the issue by
membrane technologies is
that some componentsof the
cleaning solution may be
removed along withthe
contanumnts. If this
Lippens, chemicals \till have of approsinlately every three
to be addedto the bath before to four monllls because of
it can be reused.
Case Studies
Ultrafiltration
An Illinois manufacturerof
painted steel shelving units
clean permeate
. .. .. . . . .‘ .. . .. concentrate
cleans metal surfaces prior to With the assistance of the dirt from parts prior to hard
- painting to remove rnill oils Hazardous Waste Rcsearcll anodizing. This system
and metalworking fluids. and Information Center. originally resulted in
Parts are cleaned and Illinois, the company tested wastewater with up to 150
phosphated in a 5000 gallon and installed an ultrafiltra- nulligrams perliter of oiland
heated. aqueous immersion tion unit. Primary objectives grease, exceeding local
tank, using nonionic surfac- were to reduce waste and to regulatory limits of five
tants. and rimed witha fresh preserve product qualih. milligrams per liter for both
water spray. The pH of the oil andgrease and kerosene.
bath is maintained at 3.5 andThe ultmfilmtion process
the concentration ofthe preferentially removed A microfiltration system was
cleaner is checked regularly surfammts from the cleaning installed to remove these
(the cleaner contains both solution.However.simply contaminants. The resulting
surfactants and phosphates). adding additional chenucal solution couldbe discharged
solution wodd have resulted under current limits. Even
Although tile cllange to this in escessively high phosphate better, contaminants are
aqueous systern eliminated concentrations. The com- suffkiently removed for the
water to be reusedfor
the previously used uiclloro- adding a neutralcleaning cleaning.
ethylene dcgreasingtank, oil additive that contained the
buildup i n Ule cleaner and surfactant component in the The system, which allows 99
rinse tank were unacceptable. original clemcr. percent of water to be reused,
Tlle bath lladlo be disposed had a payback period of less
Although the ultrafiltration than three months, based on
system did require significant the cost of off-site disposal
poor product qwlity. The capital in\,estment.swings (EPOC. date unkno~vn).
spent bath was classifiedas a were achieved through
hazardous waste. andwas reduced rawv matcrials usage. Conclusion
incinerated ofT-sitc i n a plant donn time. and waste
cetncntkiln.Management disposalcosts.Ultrafiltration If you llave decided that your
costs for transportationand has e.\tcndcd the bath life to aqueous cleaning bath is not
incincration totaled approsi- over 3.5 y a w . The payback accomplislling all you had
ruately $15.000 annllall!. period was 6.9 nlonths. the
hoped for. either environ-
net present value was mentally or economically, it
$152.113. and the interest is not too late to consider
rate Of rehirtl was 17s
n A A options to nlasinuze the bath
percent (Lindsey et all. life or to recycle the bath.
1991). Kcep in mind that the more
. Microfiltration
chcnucal emulslfylng power

.. . . . . . . . .I, your cleaner has, the harder

. . . e . _
An Ohio company that
fhbricates commercial
aluuninum cook\varc uses
clean permeate aqueous cleaning followed by
a deionized rinse to remove
Figure 2: Crossflow nrenlhrunefiltrution (Prosys maclune_oil. kcroscne and
Corporution, 1992)
it will be to remove the
contanunants later. You may
want to consider switching to
a cleaner wilh less cleaning
abilily, and relying more on
physical mechanisms suchas
agitation, sprays and

4

lfyou are in the nlarket for a
new aqueous cleaning
system, consider recycling
alternatives atthe Same time.
References/
Sources of
Information
Batutis, Edward. 1989.
"Keep Your Cle.m.m Clean."
Products Finishing October,
1989.
Cuslmie, George C., Jr. 1994.
Pollution Preventionfor and
C7ontrol Technolomfor
Plating Operations. National
Center for Manufacturing
Sciences, Ann Arbor, MI.
Durkcc 11. Jolm B. 1994.
"Aqueous Claning: Is it for
you?" I"voducts Finishing.
August. 1994.
EPOC Filtration and
Separation System. Date
unknown. Application
Report: Industrial Wastewa-
ter Recycle, #9002. EPOC
Filtration and Separation
Systems.
The Instituteof Advanced
Manufacturing Sciences.
1994. A Pollution Preven-
tion Resource Adanualfor
Metal Finishers. The
Instihlte of Advanced
Manufacturing Sciences,
Cincinnati, OH.
1991. "Recovery of an
Aqueous Iron Phosplmtind
Degreasing Bathby Ultrafil-
tration." Air R. IParte. Vol.
44. May 1994.
PRC Environmental Man-
agement. Inc. Hazardous
Waste Retluction in the h,fetal
Finishing Indust;. Norcs
Data Corpont'1011.
6 conversation with Ed Smiley.
..
Peterson.Dave.1995.
"Microfiltration of Aqueous
Cleaner Solutio~ls."Plating
and Surface Finishing. Vol.
82. No. 4. April. 1995.
ProsysCorporation.1992.
Technical Bulletin: (.kneral
M e n h - a n e Filtmtion. Prosys (ultrafiltration. filtration)
Corporation. IssueNo. 9 1-04,
Tcmple.Steplicn. 1990. "A
New Era for Aqucous
Cleaning." Pt-orlucrs
Fjni.vhing. March. 1990.
U.S. EPA. 1991. .-Iltet-natives
to Chlorinated Solventsfi~r
Clenning andDcgrcming.
EPN625/R-931016. U.S.
EPA. Waslungton. DC.
August 18, 1994. telcpliolie
conversation with Jiln
Kavanagh. Engineer. Licon.
Inc.9111477-0331.Anolhcr
contact for Licon is John
Campbell. Sales Reprcscnta-
tiye.
August 18. 1994 tcleplionc
conversation with Ton1
Widen, Sales Representa-
tive, US.Filter Corpont'
< Ion.
41217724014.
August 22, 1994. telephone
convemtion with Scott
Striker, District Manager.
Osmotics. 8001848-1750.
August 25, 1994 telephone
PRaSep, 7041867-2651.
Vendors
Alfa Lava1 Separation, Inc.
955 M a r s Road
Wanninter. PA 18974
215/4433030
Aqualogic
20 Devinc Strect
North Havcn. CT
20312883308
(ultrafiltration.)
Atotech
2 Rivenicw Drive
P.O. Bos 6768
Somcrsct. NJ 08875
1180OPLATING
(filtration)
Baker BrothersSystem
44 Campanilli Parkway
StoughtonMA 02072
617/314-1700
(filtration)
DJM Industrial
10440 Travis St.
Walton. KY 4 1094
(ultraliltration. filtration)
+
Fact Sheet
EPOC Fi1tra:io:: 2nd
Separation Systems
3065 North Sunnyside
Fresno. CA 93727
290129 13926
(separation, membrane
technology)
Hawken Technologies
463 Turner Dri\.e, Unit 103
Durango. CO S 1301
3031247-4655
(ultrafiltnricr:)
Hvdc Product. h c .
28045 Raru~eyFarh,.a\.
Cleveland. OH 14145-1 1SS
216/871-1188
Fax 2161871-I 113
(ultrafdtntion. sepmtion)
Industrial Filter
5900 West Ogden Avc:lue
Cicero. IL 60650
7081656-7800
(filtration)
ionics.
:!x.
6 5 G ~ o \ cS.-::.
Watetlow:. h T . 4 ;'21?2
6 171926-2400
(filtratioil)
Iverson Industries
9799 Princeton-Glendale
Cincinnati. OH 15246
(filtration)
Jan.is Manuf;:.c!::rir:g
i?5 Spacc Pnri. -s21.::::
Nasln.il!c. TX " 3 i 1
6lS/7S;-'ot::
(filtration)
3
Pollution Prevention
Extending the Life of Aqueous Cleaning Solutions

JW I Napco. Inc. SERFILCO This is the thirtyfirst in a

2 155 112th Avenue Plytlouth Industrial 1777 Shenner Road series of fact sheetsOhio
Holland, MI 49121 Napco Drive Nortllbrook, IL 60062 EPA has prepared on
6 161772-90 11 Terryville, CT 06786 118001323-5431 pollution prevention. For
(filtration) 2031.589-780 (ulu,atiltration. filtration) more information, call the
(filtration) Oftice of Pollution Preven-
Kinetic0 Engineered Systems U.S. Filter Corporation tion at 6141644-3169.
10845 Kinsman Road Osmonics 181 Thorn Hill Road
Newbury, OH 41065 595 1 Clanvater Drive Warrendalc, PA 15068
216/561-5397 MiNletoIlka. MN 55313 1 12/772-0011
(ultraliltration. filtration) 1/800/138-6766 (filtration)
(ultrafiltration. filtration. The Office of Pollution
Kock Membrane separation) Prevention wrwcreated
Systcms. Inc. to encourage multi-
850 Main Street Pasco media pollution preven-
Wilminglon. MA 0 1SS7 Byme Building tion activities within the
1/s00/343-0199 Lincoln and Morgan state of Ohio, including
(ultrafiltration) Phoeniwille. PA 19160 source reduction and
2 151983-9585 environmentally sound
Konlline-Sanderson (filtration) recycling practices. The
12 Holland Avenue office analyzes, develops
P.O. Box 257 Pcnfield LiquidTratlncnt and publicixs informa-
Peapack, NJ 07977 Systems tion and data related to
9081234-1000 8 West Street pollution prevention.
(ultr,afiltration. filtration) Plantsville. CT 06179 Additionally, the office
2031621-9141 increases awareness of
Membres. Inc. (ultrafiltration) pollution prevention
155 Route 46 West opportunities through
Fairficld. NJ 07001 PllaSep education, outreach and
2011575-8388 11 11Jenkins Rd. technical assistance
(scpantion. ultrafiltration) Gasto~Ua.NC 28052 progarns directed
7041867-265 1 toward business,
Memtek (separation) government and the
28 Cook Street public
Bileria, MA 01821 ProSys Corporation
5081667-2828 187 Billeria Road
(filtration) Chelmsford. MA0 1824
5081250-4940
Met-Pro Systems (nltraflltration)
160 Cassell Road
I-hrleysville. PA 19138 Sanborn
(filtration) Wrentluni. MA
118001343-3381
Met-Pro I Sethco (ultrafiltration)
Haoppauge, NY
5161435-0530
(filtration)

6
 United States Office of Research and EPN625/R-93/015
EnvironmentalProtection February
Development 1994
Agency Washington DC 20460

6EPA -- Guide to Cleaner

Technologies

Organic Coating Removal

Available Cleaner Technologies forCoating

Removal: Descriptive Aspects and Operational
Aspects
 I
- 1 . . . . . . . . . . . . . . . . . . . . . . . . . . .

..... . . . . . . .

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8
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.... . . . . .

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I. . . . . .. . . . . ... . .. .. . "

. . - . . . . . . . . .
I....

. .

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....... . . . . . ... . . . . .

... . . . .....

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 m
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.- 0)
0)
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F

.. . . .. . ..

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.. .. . . ..

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. ... . .. . .. .

11
E
 E

c
m
.-
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-
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0
8

m
c
 F O R TOMORROW
Supercritical CO2-an Environmentally Acceptable Alternative
for Industrial Cleaning Applications
Alternative cleaning technologies
are needed to helpindustry comply
with the international phaseout of
CFCS.
Chlorofluorocarbons (CFCs) have been
used by industry for decadesto clean
organic and particulate contaminants
from metals, plastics, composites,cerarn-
ics, electronic components, andother
uid C 0 2that cleans c&ztmin&&fiomh variety of components. h e inset photo shows
the system’s working chamber. (Photos courtesy of L o s Alamos National Laboratory)
materials. CFCs are suspected of depleting
the stratospheric ozone layer, which pre-
vents damaging solar ultraviolet radiation
from reaching theearth’s surface. Because
of the environmental implicationsof con-
tinued use of CFCs, the UnitedStates has
joined other nationsin calling for a halt to
CFC production by the end of the century.
The CFC phaseout has spawnedthe devel-
opment of a number ofalternativecleaning
technologies to meet the needs ofindustry.
Although several solvents have been
identified as substitutes for CFCs, they
appear unableto accomplish the “precision
cleaning” required in applications preva-
lent in the computer,aerospace, and medi-
cal industries. Additionally, they carry
environmental hazards oftheir own.
One new technology-supercritical fluid
cleaning-has been identified as a viable,
environmentally benign precision cleaning
technology.Three national laboratories -
have joinedfour industrial partners and the
Industrial Waste Reduction Program inthe
U.S. Department of Energy’s Office of
Industrial Technologiesto form the Joint
Association for the Advancementof
SupercriticalTechnology (JAAST).
The JAAST programis addressing the
technical challenges of developingsuper-
critical fluid systems and is working
toward commercializinga specific tech-
nology-supercritical carbon dioxide
(CO,)cleaning-for use in government
and industrialinstallations. To t h ~ send,
JAAST membersare developing the
necessary data to measure theapplicability
of supercritical cleaning and to evaluate its
economic feasibility.
Thejoint governmenthdustry
group is investigating supercritical
CO2 cleaning for a number of
applications.
In a supercritical CO, cleaning system, the
components to be cleanedare placed inside
a chamber. Liquid C 0 2is compressed and
heated; the C 0 2becomes supercritical at a

Unat
Separate
upercntical CO, is pumped into a chamber where it cleans components;the C02
temperature of 89°F (3 1.7"C) andpressure
of 1095 psi(3548 kPa). Beyond this point,
the gas and liquid phasesof the CO, are
indistinguishable. The supercriticalfluid is
pumped into the chamber where it cleans
the component. The CO,exiting the cham-
ber is allowed to expand into a gas, and the
contaminants areseparated out. The gase-
ous CO, is theneither vented or cooled
and condensed intoa liquid, which is
recycled back intothe system.
The members of JAAST work in close
coordination.The national laboratories-
Los Alamos, Sandia, and Pacific North-
west (PNL)-are conducting the basic
research. Hughes Aircraft Company,
Boeing Aerospace andElectronics
Engineering, and IBMare supplying the
parts to be cleaned and ancillaryresearch;
Autoclave Engineersis supplying the
cleaning equipment.
Research at Boeing is currently focusing
on cleaning printed wire boards. Forthis
project, supercriticalCO, cleaning will
take place at Los Alamos, initially on a
small scale. The goal is to determineopti-
mal conditions for cleaning both organic
This document was produced for theUS. Department of Energy (DOE) by the
National Renewable Energy Laboratory,a DOE national laboratory. This document
was preparedfor the Office of Industrial Technologies in conjunction with Energetics, Inc.
DOWCH10093-201 DE93000066 June 1994
Compress
Cool Vent
t tons) of CFCs per year used for cleaning in
and inorganic contaminants from the
boards. Full-scale boards will then be
tested in a SuperScrub'" unit-a new,
large-scale cleaning system recently
developed by Autoclave En,'Olneers.
Hughes Aircraft is conducting particulate
removal studies and is evaluating recy-
cling the CO, solvent during the cleaning
process. Hughes researchers are conduct-
ing these studies at Los Alamos, where
special "clean" rooms are available for
handling the test surfaces. Thegoal of the
recycle evaluation effort is to determine
the degree ofcleanliness of the CO,
required for reuse. Hughes is also studying
other supercriticalfluids that may be
viable in precision cleaning applications.
The other members of JAAST are involved
in a variety of related projects. IBM is
investigatingthe cleaning of organic,
inorganic, and particulate materials from
porous metalparts. Sandia is studying
some of the physical and chemical processes
involved insupercriticalCO, cleaning.
PNL researchers are performing bench-
scale experiments using Boeingparts.
supercritical coz cleaning is both
environmentally and economically
attractive.
The environmental advantages aloneof
supercritical CO, cleaning over CFC-based
cleaning are sufficient to make the new
technology attractive. The majorityof the
approximately 100,000 tons (90,000 metric
the UnitedStates is eventually released
to the atmosphere. This waste wouldbe
eliminated withthe use of supercritical
CO, cleaning. In addition, the oil used to
produce CFCs would besaved.
A supercritical CO, cleaning system also
has a number of economic advantages over
a conventional cleaning system. The CO,
system hasa lower capital cost, requires
less labor, canbe installed in less space.
and operates with a shorter batch cycle
time. However,the principal economic
advantage over CFCs is theestimated sav-
ings of hundreds of millions of dollars in
solvent costs.
The JAAST program is expected tobe
completed by the end of 1994. Hughes
Aircraft and Autoclave Engineers have
already formed a venturepartnership to
market the technique.If the current proj-
ects prove successful, several other com-
panies are planning to commercialize
supercritical CO, cleaning equipment.
4s Printed with a renewable
C sour& ink on paper containtng
at &ea
st W A wastepaper
 United States Office of Research and EPN625/R-93/016
Environmental Protection Development February 1994
Agency Washington DC20460

GEPA -- Guide to Cleaner

Technologies

Alternatives to Chlorinated
Solvents for Cleaning and
Degreasing

Available Technologies: Supercritical Fluids

 above its critical temperature (31.IoC,or 88.0°F), it
becomes a supercritical fluid. Typically, however, the
term supercritical (SC) is applied to any region in phase
space that is above either the critical temperature (TJ
or the criiical pressure (PC).Critical and supercritical
Supercritical Fluids fluids are excellent solvents for dissolving many
medium-molecular-weight, nonpolar or slightly polar
Pollution Prevention Beneffts organic compounds.

The main advantage of using carbon dioxide (CO,) as

a supercriticalfluid (SCF) is that CO, is nonpolluting.
CO, is derived from the atmosphere and is not created
for use as a solvent. Furthermore, the small quantity of Figure 1 is a phase diagram for CO, that shows its
CO, released would havean insignificant effect on stable phase boundaries, including the supercritical
global warming. On the other hand, cosolvents, which region. The solvent power of supercritical fluids in-
may be used to improve the solvent power of CO,, may creases as the density of the fluid increases. The
have pollution potential and should be investigated density of SC CO, can bemade nearly liquid-like at
before use. Energy is required to operate the pumps moderate pressures. The shaded region in Figure 2
and temperature control equipment that are needed in shows the pressure-temperature (P-T) region thatis
supercritical cleaning equipment. most useful for cleaning. Fluid densities range from
approximately 0.2 to 0.8 g/cm3. Figure2 shows how the
How Do They Work? fluid density may be vaned to achieve a broad range of
solvating ability.It may be said that supercritical fluids
CO, compressed aboveits critical pressure (73.7 bars, can be “tailored to achieve a desired solvent capability.
or 1077 psi) becomes a critical fluid, and if also heated

Temperature
Gases
Source: Airco (OF)

Figure 1. Phasediagramforpure CO,.

25
 Temperature ("C)
"

500
400

300

-2
150
a
I-
3
m
m
100
n
74

90

10

.25 .50 .75 1.o 1.25

Schneider,
Source: 1978 Density (g/mL)

Figure 2. Pressure-density diagram for pureCO,; temperature in O C ; cp = critical point.

Other factors that affect the cleaning abilities

of SCFs Pressure pumpto elevate CO, liquid pressure
are their gas-like low viscosity and high diffusivity, Hot water bath to elevate line temperature to that
which enable them to penetrate into small confined of the cleaning chamber
spaces, such as cracks and blind holes. In the P-T Cleaning chamber where parts are cleaned
region of interest (shaded area in Figure 2) viscosities Pressure reduction valveat fluid exit port
are about twice thoseof the gasat atmospheric Separator vessel to collect contaminants
pressure and at thesame temperature, whereas Air flow meter to monitor
CO, usage.
diffusiviiies are about30 times smaller (Lira,1988).
However onceCO, molecules have solvated contami-
nant molecules, the kinematic properties of the fluid
may change, especially near the SCFkontaminant
interface. With this change, the solvated contaminant Samples to be cleaned are placed in the cleaning
species may be difficult to remove. In practice, some chamber, which alsois called anextraction vessel or
sort of mixing mechanism or flow control usually is builtautoclave. The processis started by drawingCO, from
into the extraction vessel. the gas cylinder, then pressurizing and heating the CO,
to the sameP-Tconditions as in the extraction vessel.
A typical SCF cleaning system consists of the followingHeat tape may be wound around all critical fluid
components: transfer lines, and temperatures should be monitored at
various points by thermocouples.SC CO, flows
CO, source (compressed gas cylinder) through the cleaning chamber where it dissolves and
Chiller to condenseCO, gas to liquid carries away soluble substances. After extraction, the

26
 - ~~ ~~

CO, and dissolved contaminants pass through a cost eff eCtiVeto purchase lower-pressure-rated equip-
pressure reduction valve where pressure is dropped ment and operate the SCF system for longer timesat
below PC,arid then they enter the separator vessel. As lower pressure. The expense of supplyingCo, to the
CO, returns to the gaseous state, its solvent power system, however,is quite small, about 7 cents per
decreases substantially and contaminants drop of out pound.
solution and remainin the separator vessel. The CO,
continues to flow out of the separator vessel through Applicationa
flow meter and tothe atmosphere.
Supercriical fluids have been used in organic chemical
As a ruleof thumb, to achieve good solvency at analysis equipment andin the food and flavor indus-
moderate temperature, the fluid pressure should be 2 tries. SCFs have been used to clean and degrease
or more times the critical pressure of thefluid. Typical precision partsin the defense industry since the mid-
operating conditions for SCF cleaning equipment are 1980s.
listed in Table 7.
Supercriical fluids have been used to remove machine
Table 7. TypicalOperatingConditions for Supercritical CO, coolants on aluminum and stainless steel substrates
Cleaning
(Salerno, 1990). The cleaning process, performed at
Engineering
Parameter
Units
Units
Scientific 35OC, 138 bars for15 to 30 minutes, yielded a residual
Pressure (gauge) 100-300 bars 1.450-4,350psi
0.65% of the coolants on the substrates. The solubility
Temperature 40-85°C 100-185°F of the coolants ranged from about 1 to 5% under these
SC CO, Density 0.5-0.8 g/cm3 30-50 IblV conditions.
SC CO, Flow Rate 1-5 kghr 2-11 ibhr
lime 0.5-3hours 0.5-3 hours Benefiis

Low viscosity and high diffusivity permit SCFs to clean

Operating Features
SCF cleaning exploits the marked improvement of the
solvent powerof CO, or other substances after they
undergo a phase transition from a gas or liquid phase
to become supercritical fluids. SupercriticalCO, has
been used very successfully to remove organic of soils
moderate molecular weight and low polarity. Supercriti-
cal CO, does not give good results for soils that are the danger ofa pressure vessel or line rupture. How-
ionic or polarin nature, suchas fingerprints.
within very small cracks and pore spaces. The solvent
power of SCFs is pressure-dependent, makingit
possible to extract different soils selectively and
precipitate them into collection vessels for analysis.
Limitations
Health and Safety. The only major safety concernis
ever, the pressures usedin SCF cleaning are well
within the strength limits of most standard autoclave
equipment.

Compatibility with Materials. SCFs are compatible

SCF cleaning is probably best reservedfor removing with metals, ceramics, and polymers such as TeflonTM,
small amounts ofsoil from parts that require a high high-density polyethylene, epoxies, and polyimides.
degree of cleanliness. For example, precision cleaning SCFs cause swellingin acrylates, styrene polymers,
operations havebeen performed successfully on the neoprene, polycarbonate, and urethanes (Gallagher
following devices: gyroscope parts, accelerometers, and Krukonis, 1991). Components that are sensitive to
thermal switches, nuclear valve seals, electro- high pressures and temperatures should be not
mechanical assemblies, polymeric containers, optical cleaned by SCF methods. Process developments in
components, porous metals, and ceramics (Gallagher the future probably will make SCF cleaning more
and Krukonis, 1991; Woodwell, 1993). The cleaning aggressive toward removing cross-linked polymeric
technology is available commercially. materials and displacing particulates.

Capital costsfor installing SCF equipment are high, at Cleaning Efficacy. The major deficiencies of SCF
least $IOOKfor small-capacity equipment. The cost of in removing
cleaning are that SCFs are not effective
the autoclave increases considerably with size. Small inorganic and polar organic soils, nor do they remove
vessels may be only 1 literin volume and are relatively loose scale or other particulates. For these reasons,
inexpensive. Large vessels-30 liters, forexample- the soil mustbe well characterized to ensure its
are many times more expensive for the same pressuresolubility in SCF before an investmentis made in this
rating. If large partsare to be cleaned, it may be more technology.

27
It also is not known whether the process can remove a
complex mixture of contaminants. Therefore, a detailed
analysis of the contaminants must be done before the
likelihoodof success canbe determined.

References
Airco Gases. N.D. 474 Mountain Avenue, Murray Hill,
New Jersey 07947.

Gallagher, P. M., and V.J. Krukonis. 1991. “Precision

Parts Cleaning with Supercritical Carbon Dioxide.”
Proceedings of the 1991 International CFC and
Halon Alfernaiives Conference. The Alliancefor
Responsible CFC Policy, Baltimore, Maryland.
pp. 262-271.

Lira, C. T. 1988. “Physical Chemistryof Supercritical

Fluids: ATutorial.” In:6. A. Charpentier andM. R.
Sevenants (Eds.),Supercritical Fluid Extraction and
Chromatography.American Chemical Society,
Symposium Series No. 366. pp. 1-25.

Salerno, R. F. 1990. “High Pressure Supercritical

Carbon Dioxide Efficiencyin Removing Hydrocar-
bon Machine Coolantsfrom Metal Coupons and
Components Parts.” In: Solvent Substitution- A
Proceedings/Compendjumof Papers. DE-AC07-
761D01570, U.S. Department of Energy, Office of
Technology Development, Environmental Restora-
tion andWaste Management; andU.S. Air Force,
Engineering and Services Center. pp. 101 -110.

Schneider, G.M. 1978. “Physicochemical Principlesof

Extraction with Supercritical Gases.”Angew. Chem.
Int. Ed. Engl., 1 Z716-727.

US. Environmental ProtectionAgency. 1991. Eliminat-

ing CFC-113 and Methyl Chloroform in Precision
Cleaning Operations. EPA/401/1-91/018. Prepared
by the Industrial Cooperative for Ozone Layer
Protection Technical Committee andU.S. EPA,
Washington, D.C.

Woodwell, R. 1993. Personal communication from

Robert Woodwell of Honeywell Space Systems
Group to Bruce Sass of Battelle. September
21.
 United States Office of Research and EPA/625/R-93/016
EnvironmentalProtection February
Development 1994
Agency Washington DC 20460

&EPA -- Guide to Cleaner

Technologies

Alternatives to Chlorinated
Solvents for Cleaning and
Degreasing

Available Technologies: Carbon Dioxide Snow

 How Does It Work?

Gaseous or liquid CO, is drawnfrom a room-tempera-

ture gas cylinderor high-pressure dewar and expanded
through a nozzleto produce fine CO, particles andCO,
snowflakes and are
gas. These particles are dry ice
propelled by the gas stream.

The CO, gas or liquid is expanded through a special

CO, at
nozzle to form a jet. For example, when liquid
750 psi is throttled through a nozzle and expanded into
a volume at1 atm pressure,it undergoes a phase
change to thesolid state. The shape and size of the
snowflakes depend on the configuration of the nozzle
and the conditionsin which the flake formed in the gas
stream. The snowflakes can be individual crystalsor
collective groupingsof crystallites.

Cleaning action is performed when the snow particles

impact a contaminated surface, dislodge adherent
contaminant particles, and carry them away in the gas
stream. The processis effectivein removing very small
(submicron) particles, where fluid drag normally
restricts the performanceof liquid phase cleaning. The
CO, snow cleaning process also is believed to attach
hydrocarbon filmby dissolving hydrocarbon molecules
in a temporal liquidCO, phase at the film-substrate
interface (Whitlock, 1989). The dissolved
film is then
carried away by subsequent flow of snow and gas.

Operating Features

A complete system includes CO, a purifier, a pneu-

matic actuated head,and'a microprocessorLbased
timing circuit. Several modelsof manual spraybooths
are available that provide a nitrogen-purged, heated,
and monitored environment for CO, spraying that cost
$10K to $15K. Onecommercial purifier is available in a
17 x 14 x 24 1/2 inch stainless steel cabinet.
It weighs
135 Ib and requires an energy supply6 of A, 115 VAC,
and 60 Hz.

Another commercially available purifier is capable of

purifying CO, to a water content of less than20 ppb by
weight. In laboratory analysesof CO, before and after
purification, the hydrocarbon contentof 1800 ppb by
weight was reduced to3 ppb hydrocarbon;CO, with
140 ppb by weight halocarbons was purified to 1 ppb
Carbon Dioxide Snow wt halocarbons.
25%
duty
purifier
The
a
works
on
cycle, allowing use for 1 minuteto every 3 minutes of
Pollution Prevention Benefits recovery
time.
The
snow
gun
consumes 0.6 Ib of CO,
per minute when used continuously.
Chilled CO, is a nontoxic, inert gas that replaces
solvent use to eliminate ozone-depleting substances. Ifthe dust or dirt particles removed by CO, snow
Becausethe CO, isrecycled,thereisnoneedforcleaningareahazard,theycanbecollected by-an
disposal, nor is any wastewater produced. It generates electrically charged curtain (Hoenig, 1990).
no hazardous emissions.

28

c
 Application
CO, snow gently removes particles smaller than 10
microns in diameter down to 0.1 micron that are difficultinclude
to remove using high-velocity liquid nitrogen. It is used
to remove light oils and fingerprints from mirrors,
lenses, and other delicate surfaces, and from precision
assemblies, without scratching the surface.
CO, snow can clean hybrid circuitry and integrated
circuits without disturbing the bonding wires. This
unique ability cannot be duplicated by any other
cleaning mechanism.In the discdriie industry, CO,
snow is usedto remove particles from discs without
damage to the operation (Hoenig, 1990).
The processis used to remove paste fluxes in solder-
ing.If the grease cannotbe removed withCO, snow
alone, a cornkinationof CO, snow and ethyl alcohol is
effective, followed byCO, snow alone to remove the
impurities from the alcohol (Hoenig, 1990).
CO, is used to remove hydrocarbons and silicone
grease stains from silicon wafers. Wafers artificially
contaminated with a finger print, a nose print, and a
thin silicone grease film were found to have surface
hydrocarbon levels25 to 30% lower afterCO, snow
cleaning than the original wafer surfaces (Sherman and
Whitlock, 1990).
Layden andWadlow (1 990) report a reduction of zinc
orthosilicate concentration on a silicon wafer of more
than 99.9% after cleaning by high-velocity CO, snow.
Whitlock (1989) reports removal of greater than 99.9%
for particles ranging from 0.1 0.5to micron diameter.
In the fieldof optics, CO, snow is used to clean the
light-scattering particles and debris from the mirrors of
the world’s largest and most expensive telescopes.
CO, snow also is used to clean surfaces exposed to
contaminants in air priorto surface analysis. The
process was found to work better than solvents to
clean vacuum components. Because the aerosol couldReferences
penetrate narrow spaces, no disassembly was re-
quired, greatly shortening the time required for clean- Hoenig, S.A. 1990. “Dry Ice Snow asa Cleaning Media
ing. Furthermore,CO, cleaning is effective on some
plastic parts that cannot be cleaned by solvents
l (Laydenand
Wadlow, 1990).
29
Benefits
Some of the major beneficial aspects of CO, snow
CO, snow performs ultrapure cleaningof light oils
down to submicron size on the most delicate,
sensitive materials ranging from bonding wires to
precision mirrors in telescopes.
The CO, snow crystals generated by the snow
gun are extremely gentle.
The CO, snowflakes are adjustable to a wide
range of size and intensity.
The process does not create thermal shock, is
nonflammable and nontoxic, and causes no
apparent chemical reactions.
Cleaning by CO, snow is noncorrosive and
leaves no residue.
CO, snow does not crack glassor other ceram-
ics.
No media separation system is needed, nor is
there a media disposal cost.
CO, snow can penetrate the nonturbulent area to
dislodge contaminants and can be used on
components without disassembly that otherwise
must be disassembled because the aerosol
penetrates narrow spaces.
Limitations
Potential hazards and limitations of CO, snow include
Heavier oils, aloneor mixed with light oils, may
require chemical precleaning and/or heating to
be completely removed.
The CO, must be purified because of its ten-
dency to dissolve contaminants from the walls of
tanks in which it is stored. Purification equipment
adds expense to the CO, snow cleaning system.
When surfaces are excessivelychilled by long
dwell times, airborne impurities may condense
and settle on the clean surface (Zito, 1990).
CO, snow has low Mohs hardness and will not
. scratch most metals and glasses. However, hard
particulates suchas sand that may be present on
a surface potentially could cause scratching
when they are carried by the gas stream.
for Hybrids and Integrated Circuits.”Hybrid Circuit
Technology,December, p. 34.
Layden, L., and D. Wadlow. 1990. “High Velocity
Carbon Dioxide Snow for Cleaning Vacuum System
Surfaces.” Journal of Vacuum Science Technology,
A8(5):3881-3883.
 Sherman, R., and W. Whitlock. 1990. 'The Removal of the Fine Particle Society, Boston, Massachusetts,
HydrocarbonsandSilicone Grease StainsfromSiliconAugust 22.
Wafers." Journal of Vacuum Science Technologx
1 88(3):563-567. Zito, R. R. 1990.
with
Optics
"Cleaning
Large CO,
1jl Snow." SPlE Advanced Technology Optical Telescopes
Whitlock, W. 1989. "Dry SurfaceCleaningwithCO, IV; 12361952-971.
Snow." Paper presented at the 20th Annual Meetingof

30
 Stale of Ohio Environmental Protection Agency

STREET ADDRESS: MAILINGADDRESS:

:800 WaterMark Drive . ---.=. :5:4) 644-302C FAX: (514) 644-2322

-E.
D.O. Box 1049
Columbus. OF 432: 5.: 392 ZO~UITISUS, OH 43216-104s

Vendors of Cleaning Solutions and Equipment

September 1995
The following are tables of vendors of cleaning solutions and equipment. These tables are a partial representation.
If you wish to be added to the tables, please notify the Ohio EPA Office of Pollution Prevention in writing. These
tables are not an endorsement or approvalof these vendors by Ohio EPA.

Cleaning Solutions
Vendor
Hydrocarbon
Terpene
Alcohol
3D, Inc. X X
ADF Systems, Ltd. X
Advancetl Research Technologies X
Ambassador Marketing X X
Altos Engineering, Inc. X
ARC0 Chemical Co. X X
Ardox X X X
Ashland Chemical X X
BioChem Systems X
Blue Wave Ultrasonics X
Branson Ultrasonics Corp. X
Brulin Corporation X X
Buckeye International, Inc. X
Calgon Corp. X
Chemical Solvents Inc. X X
Chem-Tech International X X
Chemtronics Inc. X
Circle-Prosco, Inc. X X
Conceptronic, Inc. X
CRC Industries, Inc. X X
Creative Enterprises X
Crest Ultrasonics X
Dell-Chemical Systems Inc. X X
Delta Omega Technologies, Ltd. X
Dextrex Corp. X
Dow Chemical Co. X X X
Dubois ChemicalInc. X X
Dynamold Solvents, Inc. X
Ecolink X X
Eco-Systems X
Electolube Corp. USA X
Envirosolve X X
ETUS, Inc. X X
EXXON Chemical Co. X
EZE Products Inc. X X X
Fine Organics Corp. X X

EPA 1613 (rev. 1/95) George V. Voinbvich, Governor

@ Printed on Recycled Paper
Donald R. Schregardus, Director
 Cleaning Solutions continued
Vendor
Hydrocarbon
Terpene
Alcohol
Fremont Industries. Inc. X
Gray Mills Corp. X X
Hubbard-Hall, Inc. X X
Hurri-Kleen Corp. X
Inland Technologies X X X X
Insitu Environmental Chemical Co. X X
Kleer-Flo Co. X
Kyzen Corp. X X
Loctite Corp. X X
MacDermid, Inc. X
Man-Gill Chemical X X X
McDermott X X X X
North American Environmental Oil X
& Cleaning Supply Co. X
Oakite Products, Inc. X
Parker-Amchem X
Petroferm Inc. X X
P-T Technologies, Inc. X X
Qual Tech Enterprises, Inc. X
Ransohoff Co. X
Risson Group Inc. X X
Rochester Midland Corp. X X
Selig Chemical Industries X X
SONICOR Instrument Corp. X
Storchem Inc. X X X
Sunshine Markers,Inc. X
Tech Spray Inc. X X X
Terpene Technologies Inc. X X X
Texo Corp. X X
Ultrasound Fabrication, Inc. X
W.R. Grace & Co. X
Zip-Chem Products X X X X

2
 Cleaning Equipment

Vendor Semi-Aqueous
Aqueous Blasting Media Supercritical
Plastic C02 Fluids
ACCEL X X
AC Molding Compounds X

ADF Systems, Ltd. X

Alpheus Cleaning Technologies, Corp. X

Altos Engineering, Inc. X X

American Metal Wash, Inc. X
Ardox X
Automated Blasting Systems Inc.
Baron-Blakeslee, 1n.c X X
Better Engineering X
Blackstone Ultrasonic, Inc. X X
Blast-It-All
Blue Wave Ultrasonics X X
Bowden Industries X
Branson Ultrasonic lnc. X X
Buckeye International, Inc. X
CF Technologies, Inc.
Chem-Tech International X X
Cincinnati Industrial Machinery X X
Clemco industries Corp. X
Cold-Jet Inc. X

Composition Material Co., Inc. X

Conceptronic, Inc. X
Crest Ultrasonics X X
Creative Enterprises X
Crest Ultrasonics X
Deflex Corp. X
Dextrex Corp. X
Durr Industries, Inc. X
Ecolink X
Electonic Control Design, Inc. X
Empire Abrasive Equipment X

Environmental Recovery Resources,lnc. X

Envirosolutionslnc. X
EZE Products lnc. X X
Finishing Equipment Inc. X X
Gray Mills Corp. X
Hosty Equipment Corp. X
Jensen Fabrication Engineers, Inc. X
Kleer-Flo Co. X X
Kleiber & Schulx, Inc. X

MacDermid, Inc. X
Man-Gill Chemical X
Maxi-Blast, Inc.
Metal Dimensions
MPC Industries
Pangborn Corp.
Parker-Amchem X
Paul and Griffin
Proceco Inc. X

3
 a

Cleaning Equipment continued

Semi-Aqueous
Aqueous Vendor Supercritical
Media Blasting
Plastic C02 Fluids
Solidstrip, Inc.
X
hnologies, Stripping X
Ransohoff Co. X X
SONICOR Instrument Corp. X X
nc. Sonitech X X
nc. Stoelting X
Thierica X
Manufacturing
Tiyoda USA, Inc. X X
Inc.
Fabrication,
Ultrasound X X
Inc. IndustrialUnitech X X
US Technology Corp. X

4
 "

Addresses and Telephone Numbers

3D, Inc. Ashland Chemical Buckeye International, Inc.
2053 Plaza Drive Industrial Chemical & Solvents 2700 Wagner Place
Benton Harbor, MI 19022-22 1 1 Division Maryland Heights, MO 63043
800-272-4326 5200 Paul Blazer Pkwy. 314-291-1900
Dublin, OH 430 17
ACCEL 614-790-3863 Calgon Corp.
1825 E. Plan0 Parkway Chemical Technologies Group
Piano, TX 75074-8 129 Baron-Blakeslee, Inc. P.O. Box 1346
214-424-3525 1500 W. 16th St. Pittsburgh, PA 15230
Long Beach, CA 908 13 800-955-0090
ADF Systems, Ltd. 800-548-4422
P.O. Box 278 Chem-Tech International
Humboldt, IA 50548 Better Engineering 1800 Diagonal Road,Suite 600
5 15-332-5400 836 I Town Center Court Alexandria, VA 223 14
Baltimore, MD 21236 703-549-100 1
Advanced Research Technologies 800-229-3380
3 12 S. Vine St. Chemical Solvents Inc.
Park u s e , IL 60068 BioChem Systems 375 1 Jennings Rd.
708-696-937 1 14452 W. 44th Ave. Cleveland, OH 44 109
Golden, CO 80403 800-362-0693
Altos Engineering, Inc. 800-777-7870
6009 North 61 AVe. Chemtronics Inc.
Glendale, AZ 85301 Blackstone Ultrasonic, Inc. 8125 Cobb CenterDr.
602-93 1-8434 9 N Main St. Kennesaw, GA 30144
Jamestown, NY 14701 404-424-4888
Ambassador Marketing 800-766-6606
Route I-Box 207 Cincinnati Industrial Machinery
St. Davaid, AZ 85630 Blue Wave Ultrasonics P.O. Box 62027
602-720-43 10 Division of Alpheus Cleaning Cincinnati, OH 45262
Technologies Corp. 5 13-769-0700
American Metal Wash, Inc. 960 S . Rolff St.
P.O. Box 265 Davenport, IA 52802 Circle-Prosco, Inc.
360 Euclid Ave 800-3763-0144 2017 Yost Ave.
Cannonsburg, PA 15317 Bloomington, IN 47403
4 12-746-4203 Bowden Industries 812-339-3653
1004 Oster Dr. NW
ARC0 Chemical Co. Huntsville, AL 35816 Conceptronic, Inc.
3801 West Chester Pike 205-533-3700 6 Post Rd.
Newton Square, PA 19073-2387 Portsmouth, NH 03801
800-828-6627 Branson Ultrasonic Inc. 603-43 1-6262
41 Eagle Rd.
Ardox Danbury, CT 068 10 CRC Industries, Inc.
16961 Knott Ave. 203-796-0400 885 Louis Cr.
LaMirada, CA 90638 Warminster, PA 18974
714-739-2821 Brulin Corporation 2 15-674-4300
P.O. Box 270
Ardox 2920 Dr Andrew J. Brown Ave. Creative Enterprises
16961 Knott Ave. Indianapolis,PA 46206 3560 Springwood,Suite 8 1 1
LaMirada, CA 90638 3 17-923-32 11 Ponca City, OK 74604
714-739-2821 405-765-0879

5
Crest Ultrasonics Electolube Corp. USA Fremont Industries, Inc.
P.O. Box 7266 8200 Saint James Ave. 4400 Valley Industrial Park
Scotch Rd. - Mercer County Airport Elmhurst, NY 11373 Shakopee, MN 55379
Trenton, NJ 08628 71 8-565-5200 6 12-445-4 112
800-44 1-9675
Electonic Control Design, Inc. Gray Mills Corp.
Dell-Chemical Systems Inc. 4287-A SE International Way 3705 N.Lincoln Ave.
71 19 E. Shea Blvd.,Suite 106-224 Milwaukie, OR 97006 Chicago, IL 606 13
Scottsdale,AZ 85254 800-323-4548 3 12-248-6825
602-95 1-5812
Environmental Recovery Hosty Equipment Corp.
Delta Omega Technologies,Ltd. Resources, Inc. 27 Inverness Way E.
7608 Hwy 90 W. P.O. Box 36 Englewood, CO 801 12-5796
New Iberia, LA 70650 South Salem, NY 10590 303-792-5200
3 18-367-6400 914-533-6175
Hubbard-Hall, Inc.
Dextrex Corp. Envirosolutions Inc. P.O. Box 790
4000 Town Center, Suite 1 100 335 Post Rd. W. Waterbury, CT 06725
Southfieid, MI 48 175 Westport, CT 06880 800-648-34 12
313-358-5800 203-454-5902
Hurri-Kleen Corp.
Dow Chemical Co. Envirosolve P.O. Box 29
Advanced Cleaning Systems 1840 Southside Blvd. Trussville, AL 35 173
2020 Dow Center Jacksonville, FL 322 16 250-655-8808
Midland, MI 48674 904-724- 1990
800-447-4369 Inland Technologies
ETUS, Inc. 401 E. 27 St.
Dubois Chemical Inc. 1511 Kastner Place Tacoma, WA 9842 1
5 11 Walnut St. Sanford, FL 32771 800-552-3 100
Cincinnati, OH 452 12 407-32 1-7910
513-762-6839 Insitu Environmental Chemical Co.
EXXON Chemical Co. 8402 E. Redwing Rd.
Dun Industries, Inc. P.O. Box 3272 Scottsdale, AZ 85250-5740
10301 Enterprise Dr. Houston, TX 77253 602-948-9209
Davisburg, MI 48360 800-526-0749
8 10-625-5400 Jensen Fabrication Engineers, Inc.
EZE Products Inc. P.O. Box 362
Dynamold Solvents, Inc. P.O. Box 5744 East Berlin, CT 06023
2905 Shamrock Ave. Greenville, SC 29606 203-828-65 16
Fort Worth, TX 76107 800-255-1739
817-335-0862 Kleer-Flo Co.
Fine Organics Corp. 15 151 Technology Dr.
Ecolink P.O. Box 687 Eden Prairie, MN 55344
1481 Rock Mountain Blvd. 205 Main St. 800-328-7942
Stone Mountain, GA 30083 Lodi, NJ 07644-0687
800-886-82403272 800-526-7480 Kyzen Corp.
4 13 HardingIndustrial Dr
Eco-Systems Finishing Equipment Inc. Hashville, TN 372 11
345 Beckett Place 3640 Kennebec Dr. 800-845-5524
Grover Beach, CA 93433 St. Paul, MN 55 122
800-368-3700 6 12-452- 1860 Loctite Corp.
705 N. Mountain Rd.
Newington, CT 0611I
800-562-0560

6
MacDemidJnc. Ransohoff Co. Terpene Technologies Inc.
245 Freight St. N 5th St at Ford Blvd. I325 Midtown Tower
Waterbury, CT 06702 Hamilton, OH 4501 1 Rochester, NY 14604
230-575-571 9 800-248-9274 7 16-423-0670

Man-Gill Chemical Risson Group Inc. Texo Corp.

23000 St. Clair Ave. 13349 Michigan Ave. 280 1 Highland Ave.
Cleveland, OH 44 1 17 Dearborn, MI48 126 Cincinnati, OH 452 12
800-328-9745 313-581-2620 5 13-73 1-3400

McDermott Rochester Midland Corp. Thierica

2053 APlaza Dr. 333 Hollenbeck St. 900 Clancy Ave.
Benton Harbor, MI 49022 Rochester, NY 14621 Grand Rapids, MI 49503
800-272-5326 716-336-2200 616-458-1538

North American Environmental Oil Selig Chemical Industries Tiyoda ManufacturingUSA, Inc.
& Cleaning Supply Co. P.O. Box 43106 16 13 Lockness Place
270A route 46, Suite B 1 840 Selig Dr. SW Torrance, CA 90501
Rockaway, NJ 07899 Atlanta, GA 30378 3 10-539-5471
20 1-627-0722 404-69 1-9220
Ultrasound Fabrication, Inc.
Oakite Products, Inc. SONICOR Instrument Corp. 1 Maple St.
50 Valley Rd. 100 Wartburg Ave. Shelton, CT 06484
Berkeley Heights, NJ Copiague, NY 1 1726 203-924- 1624
07922 5 16-842-3344
800-526-4473 Ultrasound Fabrication, Inc.
Sonitech Inc. 1 Maple St.
P-T Technologies, Inc. 239 E. StephensonSt. Shelton, CT 06484
108 4th Ave.S. Freeport, IL 61032 203-924- 1624
Safety Harbor, FL 34695 815-235-2400
800-44 1-7874 Unitech Industrial Inc.
Stoelting Inc. P.O. Box 330
Parker-Amchem 502 Highway 67 16 South Ave.
32 100 Stephenson Highway P.O. Box 127 Wappingers Falls, NY 12590
Madison Heights, MI 4807 1 Kiel, WI 53042 800-277-5522
800-52 1-6895 414-894-2293
W.R. Grace & Co.
Petroferm Inc. Storchem Inc. Metalworking Fluids Group
54 15 First Coast Highway 3600 Billings Court, Suite 110 55 Hayden Ave.
Fernandina Beach, FL 32034 Burlington, Ontario Lexington, MA 02 173
904-26 1-8286 Canada L7N 3N6 6 17-86 1-6600
416-639-9700
Proceco Inc. Zip-Chem Products
7300 Tellier St. Sunshine Markers, Inc. 1860 Dobbin Dr.
Montreal, Quebec 15922 Pacific Coast Highway San Jose, CA 95 133
Canada, H1N 3T7 Huntington Harbor, CA 92649 800-648-266 1
5 14-254-8494 800-228-0709
AC Molding Compounds
Qual Tech Enterprises, Inc. Tech Spray Inc. So. Cherry St.
1485 Bayshore Blvd. P.O. Box 949 P.O. Box 425
San Francisco, CA 94 124 Amarillo, TX 79 105-0949 Wallingford, CT 06492
4 15-467-7887 800-858-4043 800-523-2262

7
Automated Blasting Systems Inc. Paul and Griffin
46 Schweir Rd. 907 Cotting Lane
South Windsor, CT 06074 Vacaville,CA 95688
203-528-5525 707-447-7000

Blast-It-All Solidstrip, Inc.

P.O. Box 1615 601 Interchange Blvd.
Salisbury, NC 28145-1615 Newark, DE 1971 1
800-535-2612 800-677-4568

Clemco Industries Corp Stripping Technologies, Inc.

One Cable Car Dr. 2949 E. ElvuraRd.
Washington, MO 63090 Tuscon, AZ 85706
314-239-0300 800-74 1-050 1

Composition Material Co., Inc. US Technology Corp.

1375 Kings Highway East 220 Seventh St., SE
Fairfield, CT 06430 Canton, OH 44702
800-262-7763 800-634-9 185

Embire Abrasive Equipment Alpheus Cleaning Technologies,

2101 W. Cabot Blvd.
Langhorne, PA 19047- 1893
2 15-752-8800
Kleiber & Schulx, Inc.
20 17 New Highway
Farmingdale, NY 1 1735
5 16-293-6688
MPC Industries
638 Maryville Pike, S.W.
P.O. Box 9246
Knoxville, TN 37920
800-340-7523
Corp.
9 105 Milliken Ave.
Ranco Cucamonga,CA 91730
7 14-944-0055
Cold-Jet Inc.
455 Wards Comer Rd., Suite 100
Loveland, OH 45 140
513-831-3211
CF Technologies,Inc.
1 Westinghouse Plaza, Suite 200
Hyde Park, MA 02 136-2059
(617) 364-2500

Maxi-Blast, Inc. Deflex Corp.

630 E. Bronson 3058 N. Lima St
South Bend, IN 4660 1 Burbank, CA 9 1504
800-535-3874 818-556-3335

Metal Dimensions
4720 District Blvd.
Vernon, CA 90058
213-582-1955

Pangborn Corp.
P.O. Box 380
Hagerstown, MD 2 174
1
800-638-3046