WATER POLLUTION CONTROL RESEARCH SERIES • 16080 HTZ 05/72
POLYMER FILM OVERLAY SYSTEM FOR
MERCURY CONTAMINATED SLUDGE
PHASE I
U.S. ENVIRONMENTAL PROTECTION AGENCY
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of pollution
in our Nation's waters. They provide a central source of
information on the research, development, and demonstration
activities in the water research program of the Environmental
Protection Agency, through inhouse research and grants and
contracts with Federal, State, and local agencies, research
institutions, and industrial organiEations.
Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Chief, Publications Branch
(Water), Research Information Division, R&M, Environmental
Protection Agency, Washington, DC 20460.
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POLYMER FILM OVERLAY SYSTEM FOR MERCURY
CONTAMINATED SLUDGE - PHASE I
by
Michael U. Widman
Michael M. Epstein
BATTELLE
Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
for the
Office of Research and Monitoring
ENVIRONMENTAL PROTECTION AGENCY
Project # 16080 HTZ
Contract # 68-01-0088
May, 1972
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.00
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EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents neces-
sarily reflect the views and policies of the
Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorse-
ment or recommendation for use.
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ABSTRACT
Concepts for dispensing of polymer films underwater and over mercury
contaminated sludges were generated. The candidate systems examined
were based on coagulable materials, hot melt polymer compounds, and
preformed films. A large number of laboratory blends of the candidate
materials in the first two categories were made and qualitatively
evaluated to identity promising formulations. Experimental equipment
appropriate to each concept was designed and experiments were conducted
in an 18-foot-long test tank to establish the feasibility of the material-
equipment systems.
The results of these experiments suggested that commercially available
preformed films could be successfully dispensed from a roll and applied
as an overlay on the mercury contaminated sludge.
Dialysis experiments were conducted to determine the permeability of the
candidate materials to organic and indrganic mercury compounds. Pre-
formed nylon and high-density polyethelene performed best in all cate-
gories. Microbiological and biological experiments showed that the
preformed films, and hot melt polymers were most promising.
A cost analysis showed that a preformed film overlay can probably be
deployed for 1.5 cents to 3.3 cents per square foot, hot melt films for
about 2.5 cents per square foot, and a coagulable nylon film for about
4 cents per square foot.
Based on this work the preformed film system was recommended for Phase
II implementation.
This report was submitted in fullfillment of Project No. 16080 HTZ,
Contract No. 68-01-0088 under the sponsorship of the Environmental
Protection Agency.
iii
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CONTENTS
Section
I Conclusions
II Recommendations
III Introduction
IV Description of Candidate Systems
V Discussion of Experimental Phase
VI Implementation of Recommended Approach
VII References
VIII Appendices
1
3
5
7
19
59
63
65
v
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FIGURES
PAGE
1 OVERALL EQUIPMENT ARRANGEMENT 10
2 DECK ARRANGEMENT FOR BARGE-MOUNTED APPARATUS FOR PREFORM
FILM OVERLAY SYSTEM 11
3 DECK ARRANGEMENT FOR BARGE-MOUNTED APPARATUS FOR HOT-MELT
FILM OVERLAY SYSTEM 12
4 DEPLOYMENT OF PREFORMED FILM WITH PREAPPLIED ANCHOR WEIGHTS 13
5 DEPLOYMENT OF PREFORMED FILM WITH WIRE-COIL ANCHOR SYSTEM 15
6 DEPLOYMENT OF HOT-MELT FILM WITH GRAVEL BALLAST ANCHOR
SYSTEM 16
7 DEPLOYMENT OF ALCOHOL-SOLUBLE NYLON FILM 17
8 EFFECT OF COMPONENTS ON PROPERTIES OF HOT-MELT COMPOUNDS 26
9 DIALYSIS-CELL APPARATUS 30
10 TEST TANK AND TYPICAL APPARATUS 37
11 SCHEMATIC CROSS SECTION COAGULABLE POLYMER NOZZLE 38
12 EXTERIOR OF EXPERIMENTAL COAGULABLE FILM NOZZLE 39
13 FR-S-257 BASED LATEX EMERGING FROM EXPERIMENTAL NOZZLE 39
14 DURAN 220-BASED LATEX EMERGING FROM EXPERIMENTAL NOZZLE 41
15 ALCOHOL-SOLUBLE NYLON EMERGING FROM EXPERIMENTAL NOZZLE 41
16 COAGULATED NYLON FILM FORMED IN TEST TANK 43
17 HOT-MELT DIRECT EXTRUSION NOZZLE 43
18 HOT-MELT-COMPOUND EQUIPMENT APPROACHES 44
19 ARRANGEMENT OF CONTINUOUS DRAW-DOWN APPARATUS 47
20 CONTINUOUS DRAW-DOWN APPARATUS IN OPERATION 47
21 VIEWS OF LARGE-SCALE PREFORMED FILM EXPERIMENTS 50
VI
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TABLES
No. Pa^e
1 Characteristics of Selected Hot Melt Blends 28
2 Transmission of Inorganic and Organic Mercury Through
Polymeric Films 31
3 Results of Microbiological and Related Studies of Polymer
Barriers 35
4 Summary of Preformed Film Experiments 49
5 . Estimated Basic Material Cost for Polymer Overlay 52
6 Estimated Cost of Anchoring Polymer Overlay 53
7 Estimated Cost Matrix, Material/Predeployment 54
8 Deployment Cost Summary 56
9 Summary of Surface and Subsurface Equipment Costs for
a Selected Mission 57
Vli
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SECTION I
CONCLUSIONS
The experimental program described in this report demonstrates the
technical feasibility of using polymer film barriers to isolate mercury-
contaminated sediments. Three basically different polymer-equipment
systems have been shown to be feasible for this application. The
materials are effective barriers to mercury-contaminated sediments and
specially prepared mercury solutions, have good strength, and will
provide long service life. Practical equipment concepts for each system
have been developed.
On a performance-only basis, the most effective polymer film material
appears to be preformed nylon 6 (polycaprolactam). This film is an
effective barrier to both inorganic forms of mercury (mercuric chloride)
and organic mercury (methylmercuric chloride and dimethyl mercury).
All of the other polymer films of special interest [high-density poly-
ethylene, low-density polyethylene, polyvinyl chloride, alcohol-soluble
nylon, and poly (ethylene-vinyl acetate) copolymer hot melts] have been
shown to be equally effective as barriers to mercuric chloride as the
nylon 6. However, none are as impermeable to the organic mercury
compounds as the nylon 6, and they vary considerably in their capability
of retaining these particular mercury compounds. The most effective of
these other candidate materials is the high-density polyethylene. It
is not known at this time how specific film properties such as crystal
structure and molecular orientation will affect these results, but it
is suspected that a biaxially oriented structure would improve the
barrier performance to still higher levels of effectiveness.
The preformed nylon 6 film has been recommended for further evaluation
in a field demonstration. This recommendation was based on performance
considerations only; the cost of this system, however, is about 2 to
2-1/2 times greater than the next most effective system, the high-density
polyethylene. On a total cost effectiveness, the latter may be preferable
to the nylon 6 since its effectiveness as a barrier is still many times
better than the remaining materials. In general, preformed films have
also proven to be the most attractive alternative from an equipment
concept. It is believed that developing and building equipment of this
type for eventual implementation of the barrier concept can be accomplished
for less cost and more quickly than for the other approaches.
The only material in this grouping that poses any environmental hazard
in itself, and this is believed to be very slight, is the alcohol-
soluble nylon. Deployment of this system would entail introducing small
amounts of ethyl alcohol to the lake system. The quantities involved
are not so large as to pose any real threat, but the laboratory studies
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do indicate an increase in BOD (Biological-Oxygen-Demand). This system
has one other undesirable feature - high cost. However, as with the
preformed films, a workable equipment concept for this material appears
to be fairly simple.
Hot melt films formed by casting on a rotating drum offer the greatest
opportunity for varying the physical-mechanical properties of the barrier.
The materials are inexpensive and practical to use and the equipment
concept is quite feasible. However, this system is relatively complex
compared to preformed films and its barrier properties are poorer. It
is therefore less desirable from these points of view.
Sodium alginate films, originally developed for underwater salvage use,
have been shown to be impractical for the present application,, As
suspected, they are highly biodegradable, according to our laboratory
results. It is also believed that they would not provide effective
barrier properties because of their high water content.
All of the polymer films have certain common problems. All require
regularly spaced vent-holes to permit the escape of gases formed in
the sediments, and all require some form of anchoring, even though the
specific gravity may exceed that of water.
In summary, it is concluded that the polymer film barrier concept has
considerable promise as a procedure for decontaminating water systems
with mercury-rich sediments.
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SECTION II
RECOMMENDATIONS
Promising candidate material systems and delivery techniques have been
identified in this Phase I study for overlay of mercury contaminated
sediments. One approach, that of using preformed commercial film, is
recommended for future implementation because it appears to be the most
easily implemented effective barrier with a minimum of development and
capital equipment cost. Our experiments show that commercial films are
available which can provide a wide range of cost and effectiveness.
Based on these results it is recommended that a Phase II field demon-
stration program be conducted. In the Phase II program, the following
general tasks must be accomplished.
• Select and assess a suitable test site.
• Design a test program which will permit evaluation
of the results of overlay of mercury contaminated
sediments.
• Optimize a preform polymer material.
• Design and construct application equipment.
• Place and execute a polymer overlay in the test
site.
• Evaluate the results of the experimental program
and assess their implications for further action
to overlay other mercury contaminated sites.
A plan for Phase II research program has been prepared and submitted to
the Environmental Protection Agency. A summary of the approach described
in that proposal is contained at the end of this report.
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SECTION III
INTRODUCTION
Towards the end of the 1960's and into early 1970, commercially caught
ocean fish species, as well as inland freshwater species, were found to
contain excessive amounts of mercury. As a result, many lakes were
closed to commercial fishing, and catches of selected species of salt-
water fish were restricted. This led to a fairly comprehensive search
by Federal and State authorities to determine the source of this mercury.
The sediments of many major inland lakes and streams were found to
contain large amounts of mercury, the result of years of dumping by
industrial and other users of mercury. Government and industry action
since that time has resulted in considerable progress in reducing the
inflow of additional mercury contaminates, although the inflow has not
been completely abated.
The large quantities of mercury in lake and stream sediments remain a
major environmental problem. To deal with this hazard, the Water Quality
Office of the Environmental Protection Agency solicited research programs
to conduct research and to develop new and effective methods and technol-
ogy for the control of pollution from these sediments. The study described
in this report is a part of that program.
The objective of the Battelle-Columbus Phase I program was to determine
the merits of isolating mercury contaminated sediments with barriers
constructed of a polymer film and to indicate the most promising method
to accomplish this end. Two interrelated goals had to be satisfied:
(1) Identify polymer film material systems capable
of providing mercury compound barrier properties,
and
(2) Develop equipment design concepts for dispensing
the polymer films over the contaminated sediments
and experimentally verify the feasibility of the
material-equipment system in the laboratory.
The program was accomplished by screening candidate materials in three
general categories. Coagulable materials, hot melt materials, and pre-
formed materials. Equipment concepts for these classifications were
generated and the material-equipment system feasibility verified by
laboratory experiment and analysis.
This report contains recommendations, a general description of alternative
systems, the experimental work and evaluation, and a discussion of a plan
for implementation of the recommended approach.
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SECTION IV
DESCRIPTION OF CANDIDATE SYSTEMS
The research in this Phase I program has resulted in the identification
of three promising material-equipment systems for overlay of mercury
contaminants. These range from a relatively simple system which uses
preformed film to the more complex concept which requires subsurface
machinery to continuously cast hot melt films. Although all of the
concepts have merit and appear to have the potential for successful
overlay of mercury contaminated sludge, the approach using preformed
film appears most advantageous„ In the following paragraphs the basic
principles of the material systems concepts will be described followed
by descriptions and illustrations of the surface and subsurface equipment
needed to implement these concepts.
BASIC PRINCIPLES OF THE
MATERIAL SYSTEM CONCEPT
The basic principles of the concepts are quite simple; implementation
of the concepts in the underwater environment however is considerably
more complex.
Coagulable Polymers
An alcohol soluble nylon system was investigated during this program
which appears to have almost ideal characteristics. The material is
essentially a one-part system in which the alcohol in the alcohol-
nylon solution is displaced by water when the polymer is extruded into
the water. The nylon is insoluble in water and forms a tough continuous
membrane.
Application equipment will consist of a means for pumping the predis-
solved alcohol-nylon solution to the subsurface apparatus. The subsurface
apparatus must extrude a continuous and uniform film thickness of about
0.012 inch.
The most advantageous feature of this material-equipment approach is the
simplicity of the system. The most serious drawback is the probable
high cost of materials.
Hot Melt Materials
A hot melt material-equipment system provides the greatest opportunity
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for optimization of film characteristics, especially additives such as
scavenging agents and other fillers.
Although a number of equipment approaches were tried in the laboratory,
a continuous casting process or drawing down onto a rotating chilling
surface produced superior results. Hot melt material is delivered to
the subsurface apparatus from the surface through insulated and heated
delivery lines. The subsurface dispensing equipment must be enclosed
in a "pressure" hull and be equipped with seals to prevent the entry
of water into the system.
The most advantageous characteristic of the hot melt material-equipment
system is the wide range of film properties that can be formulated into
the material and the high physical quality of the in situ formed film.
A serious disadvantage is that the dispensing equipment and support
equipment will be expensive to develop, construct, and maintain.
Preformed Film System
The development of an approach for the deployment of preformed films was
an unexpected benefit of the Phase I research. It had been decided some
time ago that this approach could not be satisfactorily implemented when
in fact the in situ film-forming methods under investigation produce the
same handling and deployment problems inherent in the preformed film
approach.
The concept involving the use of preformed film received the benefit of
the largest scale experiment in the program simply because it was easy
and inexpensive to implement. With this concept, preformed film of
commercial manufacture is unrolled from a subsurface roll of the material.
A wide variety of preformed materials can be used including such
inexpensive films as low-density polyethylene or more effective barriers
such as nylon.
As a result of experiments with preformed films, concepts for physical
stabilization of the dispensed film were generated. It is expected that
one or more of these concepts must be applied to any of the candidate
overlay systems for them to be successfully stabilized on the bottom.
The most advantageous features of the preformed film approach is the
relatively simple equipment requirements, effectiveness of available
materials, and short equipment development time required. The apparent
disadvantage is the relatively large bulk of material which must be
handled at the bottom.
Surface Support System
The overall approach contemplated for each of the candidate systems is
quite similar. Basically a film of up to 20 feet in width is to be
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deployed on the. bottom at moderate depths. Although obstructions are
anticipated, the concept is planned for relatively flat or rolling
terrain. Figure 1 is an artist conception of the overall arrangement
of the overlay deployment system.
The subsurface equipment is mounted on the end of an arm which extends
to the bottom. A convenient method of providing this support would be
to use a commercially available hydraulic crane or backhoe excavator
which can be positioned on the deck of a barge. Figure 2 shows an
arrangement of equipment or a barge which could be used for deployment
of preformed film. A hydraulic crane or backhoe is modified to provide
adequate reach and to accept the subsurface equipment. Rolls of film
are also stored on the deck of the barge,, The subsurface equipment is
designed so that it can be loaded at the last station of the storage
rack and the backhoe can swing film roll and dispenser over the end of
the barge and into the water.
Figure 3 shows how the more complex systems like the hot melt film
approach can be accommodated by a barge-mounted equipment arrangement.
In this illustration, the hot melt apparatus is connected to the
pumps and melting tank with an insulated and heated flexible pipe which
is supported in part by the crane boom., Fuel tanks, heating plant, and
basic hot melt material is also stored on the deck of the barge.
Subsurface Equipment System
The subsurface equipment concepts are quite similar for the preformed
film and the hot melt material-equipment approaches. Basically the film
is either formed on the hot melt system casting drum or unrolled from
a large roll of preformed film before it is applied to the bottom.
After the film has left the casting drum or dispensing roll, it goes
over a dancer roll which controls film tension and is applied to the
bottom under a foot roll. The foot roll is visualized as a large low
pressure tire or roller which can easily negotiate bottom contours and
discontinuities. The foot roll places the film in intimate contact
with the bottom and this action squeezes the water out from under the
film. Although this action tends to hole the film on the bottom,
experiments have shown that anchoring is required to maintain physical
stability of the film on the bottom. Several approaches to this problem
have been conceived.
Figure 4 shows how this concept would look on the bottom. In this case
a 20 foot wide roll of preformed film is being dispensed. The film has
preapplied anchor weights attached to it which have been applied at a
shore-based facility when the film was put onto the dispensing rolls.
For a 20 foot width of film a foot roll of about 6 feet in diameter
should be adequate to negotiate most bottom obstructions. "In situ"
anchoring schemes are necessary for hot melt formed films and the alcohol
solulable nylon films since the anchor weights cannot be applied before
they are dispensed.
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Barge
Film supply
Hydraulic
crane
LaKe or stream bottom
I
*
25 to 30-foot depth
FIGURE 1. OVERALL EQUIPMENT ARRANGEMENT
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Hydraulic crane
Front-and
rear-scanning
TV pods
Film roll
Dancer roll
Foot roll
Film supply
FIGURE 2. DECK ARRANGEMENT FOR BARGE-MOUNTED APPARATUS FOR PREFORM
FILM OVERLAY SYSTEM
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Insulated
Hydraulic crane flexible hose
tank
Dispensing
drum
shroud
Dancer
roll
Exhaust stack
Fuel tanks
Foot roll
FIGURE 3. DECK ARRANGEMENT FOR BARGE-MOUNTED APPARATUS
FOR HOT-MELT FILM OVERLAY SYSTEM
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Sf>
Remote-control TV pods
(scanning front and rear)
Film roll
Foot roll (low-pressuretire)
c
o
Preapplied anchor weights
FIGURE 4. DEPLOYMENT OF PREFORMED FILM WITH PREAPPLIED ANCHOR WEIGHTS
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Figure 5 shows the first of these anchoring systems being used with the
hot melt dispensing apparatus. This anchoring concept uses helical formed
wires that puncture the film. The helical formed wires are produced
continuously from wire feed from the surface. In some bottom conditions
they may actually provide a physical attachment of the film to the bottom
in addition to the anchoring function provided by their weight. Note
that independent suspension of the wire forming heads will be necessary
to accommodate bottom contours.
Figure 6 shows a gravel ballast system being used with the preformed
film dispensing unit. This approach can also be used with hot melt and
alcohol soluble nylon material-equipment systems. With this anchoring
apparatus, circumferential projections on the foot roll fold grooves or
longitudinal pockets into the film as it passes under the foot roll.
Ballast, either sand, gravel or other suitable material, is placed into
these grooves to anchor the film to the bottom. Depending upon the soft-
ness of the bottom and on the availability of ballast material, this
approach can provide a high degree of anchoring at a relatively low
cost.
The alcohol soluble nylon film system probably would be anchored with the
gravel ballast system. It is doubtful that the film would have become
hard enough so soon after formation to be anchored with helical wires.
Figure 7 shows the configuration of the subsurface apparatus for dispensing
the alcohol soluble nylon films. The gravel ballast systems have been
omitted for clarity. Note that a foot roll is not used for this concept.
The foot roll would probably adhere to or break the film because some
finite time is required for the alcohol to be displaced by the water and
for a firm, tough film to develop.
RECOMMENDED APPROACH
Although all of the concepts for material and equipment systems appear
to have the potential of satisfying the overall objective of providing
an effective polymer overlay for mercury contaminated sludge, the
approach which uses preformed films appears to be most advantageous.
An analysis of the system shows a remarkable flexibility which will be
very useful in implementation of the concept and in optimization of the
treatment for specific contaminated sediments. The analysis of implementa-
tion costs in later sections of this report shows that the preform
approach can be used to apply various polymer films at a range in cost
of about 1.5 cents to 3.3 cents per square foot. These films have a wide
range of barrier performance with respect to both organic and inorganic
mercury compounds.
Because a prefabricated anchoring system can be used with a preformed
film overlay, development of subsurface anchoring and ballasting equipment
can be deferred until after the effectiveness of the overlay approach is
verified in full scale field tests. Thus although the cost of the overlay
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Lake bottom Rim
To surface
wire supply
Wire-coil anchor
(typical)
C C. C_
Cross Section of Film
Anchored by Wire Coils
Wire-coiling and anchoring
mechanism
FIGURE 5. DEPLOYMENT OF PREFORMED FILM WITH WIRE-COIL ANCHOR SYSTEM
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Lake bottom
Film Gravel (typical)
TV
Hot-melt
dispensing
system
Foot roll
Gravity-feed
gravel hose
Cross Section of Film
Anchored With Gravel
FIGURE 6. DEPLOYMENT OF HOT-MELT FILM WITH GRAVEL BALLAST ANCHOR SYSTEM
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Insulated flexible hose
TV cameras
Nylon film
Remote
control
valve
Extrusion nozzle
FIGURE 7. DEPLOYMENT OF ALCOHOL-SOLUBLE NYLON FILM
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material will be somewhat higher, the development costs associated with
the "in situ" anchor or ballast equipment can be omitted. Additional
savings in development costs appear feasible because of the straight
forward design involved in the subsurface film dispensing apparatus.
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SECTION V
DISCUSSION OF EXPERIMENTAL PHASE
The experimental phase consisted of extensive material system develop-
ment in the laboratory, design, construction, and implementation of
large scale equipment tests. Material experiments, evaluation of
barrier and of microbiological and biological properties of these
materials and analysis of the cost inherent in the candidate systems
were also accomplished in this phase.
MATERIALS
In a previous development program sponsored at Battelle by the U.S.
Navy Supervisor of Diving, Naval Ships Systems Command (see references
1 and 2 in Section VII), the feasibility of silt stabilization was
demonstrated by in situ formation of a gelled polymer film consisting
primarily of alginic acid. This development was the initial basis for
the concept of a polymeric film barrier for mercury-containing sludge
deposits. The objective of the present program, however, differed
fundamentally from the earlier development in the requirement to retain
water-soluble species. This objective demanded films of much higher
polymer density than was possible with the gelled alginates in order
to maximize retention of the mercury compounds. All departures from
the original gelled-polymer system resulted from these considerations.
The material formulations which were developed in the experimental
phase of the program were latex systems, solvent systems and hot melt
blends.
Latex Systems
Two inherent characteristics of latices make such systems particularly
attractive for the in situ formation of barrier films: (1) low
viscosity at relatively high polymer contents (generally between 50 and
65 percent for the unmodified latex), and (2) aqueous dispersions, thus
eliminating any potential problems relating to the environmental impact
of solvents, as well as eliminating the need of putting the polymer into
solution which saves an operation that is generally necessary with
organic solvent systems. Moreover, a wide choice of polymer types is
available in latex form, usually at relatively high molecular weights
which tend to provide good physical properties in polymer films.
The same characteristics which make latices so attractive also are at
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the root of the basic problem of "in situ" film formation with these
materials: (1) ready dispersibility in the aqueous environment, and
(2) built-in stability to prevent latex coagulation during manufacture
and handling. Much of the laboratory work with latices was directed at
overcoming these problems. Other considerations included the optimization
of physical and especially barrier properties. Compounding for increased
density to counteract buoyancy is generally required for most polymer
filmso However, this is usually more easily achieved in latices compared
to melt or solvent systems.
Polyvinylidene Chloride
This polymer is known for its excellent barrier properties to gases and
vapors and is therefore widely utilized in the packaging field either
as a base film or as a coating for less expensive films. Since diffusion
in the gaseous and liquid phase are basically similar processes, it was
expected that this polymer could produce a good barrier to mercury
compounds. This material is also largely unaffected by water and has
one of the highest densities of commercial polymeric products. Both
of these factors should contribute to producing a good barrier film,
and the high density eliminates the need for fillers to overcome
buoyancy. From the chemical structure of this polymer good resistance
to the aqueous and biological environment may be predicted, which should
result in a long service life. At the same time no toxic contaminants
are expected to be released into the environment.
A commercial, high solids (61 percent), polyvinylidene chloride latex,
Daran 220, was selected for the laboratory investigation. This latex
has an initial pH of 3.5 to 4.5 which may drop further on aging. It
was, therefore, believed that an alkaline coagulating solution might be
best suited to produce films. Films were cast on glass substrates with
40-mil draw down bars. The wet films were immediately immersed in a
tray filled with the coagulating medium, and after 5 minutes the product
was transferred to a water bath.
According to the results summarized in Table A-2 (in the Appendix), a
20 percent sodium hydroxide solution, contrary to expectation, did not
produce a good film. A hydrochloric acid solution of the same concentra-
tion, however, gave very encouraging results. Unfortunately, reduction
of the acid concentration to 5 percent produced a very weak film,
indicating that a very short contact time encountered in an actual
operation would require considerable alteration of the latex properties
to overcome its stability. Other effective coagulant baths included 20
percent solutions of aluminum sulfate and of ferric chloride respectively.
In addition to the need for reducing the coagulation time, two short-
comings requiring attention were identified by the above tests: (1) the
surface of the wet films was distrubed to a considerable depth by the
immersion into the coagulation baths (identified as "rough surface" in
the tables), and (2) all films were somewhat brittle; those coagulated
with HC1 to a lesser degree than those contacted with the other baths.
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The remaining experiments shown in Table A-2 were designed to deal with
several of the problems identified above. The colloids shown in the
table include several grades of alginates, some polyanhydride resins and
vinyl acetate copolymer. Several of these colloids were quite effective
in eliminating the surface roughness described above. The alginates in
particular produce very high viscosities in aqueous systems even at 1 or
2 percent concentration. The effect of increasing the viscosity of a.
latex system is to reduce the mobility of the liquid film during the
crucial moments when coagulation is initiated. Moreover, the alginates,
and some of the other colloids as well, are gelled by acids or poly-
valent cations (including Al"1"** and Fe""^") . These chemical reactions
occur much more rapidly than the physical process of particle coalescence
involved in the coagulation of the latex. Thus a colloid-thickened
latex film on contact with the coagulation medium becomes almost
immediately embedded in a gel structure which provides the environment
in which the latex coagulation can proceed.
Of the several colloids tested, the alginates gave the best results.
There were also small differences in film strength discernible in
compositions containing different grades of alginates. In general, it
was concluded that an alginate concentration between 0.5 and 1 percent
based on latex solids gave optimum results and that Superloid was the
preferred grade.
Efforts next turned to reducing the brittleness observed in the Daran
films. The experiments in Table A-3 (in the Appendix) summarize the
progression of this work. From the outset it was discovered that many
of the recommended plasticizers affected the latex stability adversely
(see 31 series). This behavior, if properly controlled, could be
turned into an asset by improving the response of the latex to the
coagulation media. Based on the results of the early experiments
subsequent work concentrated on the use of Santicizer E-15 as the
plasticizer.
A plasticizer concentration series (36-1 to 36-4 in Table A-3) indicated
that levels of 20 percent or higher based on polymer would coagulate the
latex. Later work in the presence of colloid showed that 20 percent
plasticizer levels could be tolerated. This level of plasticizer was
also desirable from the standpoint of flexibility as well as for any
increase in coagulability it may have provided. Comparison between
films coagulated with hydrochloric acid or aluminum sulfate showed that
the.latter were distinctly harder and less flexible despite the high
plasticizer content.
Some laboratory work was also conducted in an attempt to predict the
minimum contact time between the latex composition and the coagulating
solution. For this purpose, cast films were exposed from 2 to 5 seconds
to the coagulant baths and immediately transferred into water. Exam-
ination of the strength of the surface skin was used as the basis for
judging the minimum contact time probably necessary for satisfactory
film generation. It was estimated that a minimum of 3 seconds contact
with 20 percent HC1 may be desirable and perhaps somewhat less for more
21
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concentrated solutions. On the other hand, both 20 and 40 percent
aluminum sulfate solutions gave less satisfactory results. In comparison
with the other latex systems under investigation, the Daran based
compositions continued to hold the greatest overall promise of success.
Styrene-Butadiene
Among a group of latices surveyed, a carboxylated, 50/50 styrene-butadiene
latex, FR-S 257 showed promise for underwater film generation. Film
formation occurred with 20 percent solutions of HC1, FeCLj, or A^ (80^)3.
The results given in Table A-4 (in the Appendix) show that the products
formed in HC1 had superior properties, and this conclusion was repeatedly
confirmed with later compositions incorporating various colloids. The
use of colloids was necessary just as in the case of the Daran latex in
order to protect the wet film from disruption on immersion into the
coagulants.
Unlike Daran, this polymer did not require any plasticizer to produce
flexible films„ However, its density was sufficiently low to require
the. incorporation of a filler to keep the film from flating to the surface.
Titanium dioxide was stirred into the composition at a 10 phr (parts per
hundred rubber or polymer) level and performed this function satisfactorily.
In a large-scale operation a less expensive filler such as clay or barytes
could be substituted. In our laboratory experiment the TiOo helped make
the uniformity of dispersion more visible « Grinding of the filler is not
necessary, unless long storage life is desired, since the unground filler
would settle considerably faster.
The disadvantages of films coagulated from FR-S 257 were mainly their
softness and inadequate strength. As a corollary, much longer contact
times with the coagulation media were necessary to develop coherent
self-supporting films. The experimental work to correct these short-
comings included the evaluation of several colloids in addition to the
alginates. Some of these were employed in much higher concentrations in
order to produce a maximum effect on the physical properties of the films.
Some compositions were formulated with carboxymethyl-cellulose, since
this hydrocolloid was expected to add hardness and physical strength to
the films, particularly when treated with aluminum sulfate. In order to
introduce larger quantities of colloids into the formulation, recourse
was taken to lower molecular weight products. In general, the results
did not indicate sufficient improvement to justify further development
of this system, although some gains were made with aluminum sulfate
coagulation of a composition containing Kelgin LV (see 42-6 in Table A-4).
Some formulations were also prepared containing such potential mercury
scavengers as sulfur or zinc. Sulfur presented a special problem
because of its very poor water wettability. However, this could be
overcome by treating the sulfur powder with a surface active agent before
incorporation into the compositions. It was hoped that the polymer matrix
surrounding the zinc particles would protect them at least for a brief
contact time from the effects of a dilute hydrochloric acid bath. However,
22
-------
hydrogen formation resulting in numerous bubbles in the film could not
be prevented. It will be necessary, therefore, to avoid this combination.
An unmodified synthetic rubber latex, FR-S 194, consisting of a 26/74
styrene-butadine ratio was investigated as outlined in Table A-5 (in the
Appendix). Hydrochloric acid coagulation of the latex by itself resulted
in much shrinkage. This could, however, be eliminated by adding a small
amount of alginate. Concentration studies with several alginates showed
that lower concentrations tended to give stronger films. However, the
shrinkage and surface roughness described earlier limited the amount of
reduction that could be tolerated to between 0.5 and 0.8 percent based
on latex solids. Further study of this system was discontinued because
no improvement in coagulation time or in film strength over the previously
described formulations was obtained.
Miscellaneous Latices
In addition to the systems discussed in the previous sections, a number
of other latices were briefly examined (see Table A-6 in the Appendix).
Two of these were synthetic rubber latices and three others were vinyl
chloride-based polymers or copolymers^
The rubber latices consisted of a 29/71 styrene-butadiene polymer,
FR-S 2003, and a polybutadiene, FR-S 2004. Neither of these products
showed promise for any improvement over the other rubber latices which
were studied at greater length. They were consequently dropped from
the program.
The remaining polyvinyl chloride (PVC) latices are chemically more closely
related to the Daran latex than to the rubber latices„ The first one
shown in Table 5, FPC 790, is an unplasticized homopolymer which does
not lend itself readily to film formation without further modifications,
as is borne out by the results. According to the manufacturer's recom-
mendations it requires high plasticizer levels to improve properties.
While some improvement in film quality was realized in laboratory
experiments, the results fell considerably short of what was needed.
A PVC latex preplasticized during manufacture with 35 parts dioctylphthalate,
FPC 7299B, produced considerably better results, particularly when HCl
was the coagulating agent. However, these results seem to depend on
fairly long contact time with HCl, and considerably more compounding
would be needed to shorten this time. In contrast, a vinyl chloride-
acrylic copolymer latex, FPC XR 7351, produced interesting results in
relatively short contact times, once it was modified by a colloid and a
plasticizer. This compound responded especially well to coagulation
media of higher acid content such as 50 percent sulfuric acid.
While these results point to some interesting directions for further
study, it was felt that the program objectives could be more easily
achieved with one of the other, more simple approaches. Further work
with latices was, therefore, suspended.
23
-------
Solvent Systems
From the standpoint of ease of film formation, polymers soluble in water-
miscible solvents are particularly attractive. The water environment
acts directly as the coagulating medium, greatly simplifying the delivery
system and eliminating the problems of contact time with the gelling
agent encountered with the latices. However, there are also two
inherent disadvantages associated with such systems: (1) the solvent
will contribute to the BOD and in some cases may be toxic and (2) vis-
cosity considerations will restrict the maximum polymer content below
that possible with most latices.
To explore the possibilities of such a system, an alcohol soluble nylon
terpolymer, Elvamide 8061, was selected. This polymer is known to
produce strong, tough films, and its solubility in alcohol-water mixtures
was expected to minimize the toxicity and BOD problem. Solutions were
prepared by refluxing the resin in the solvent for 2 to 3 hours. Both
methanol and ethanol could be used in combination with 10 to 20 parts
water. Eventually, however, ethanol-water systems were preferred in order
to further minimize toxicity.
As shown in Table A-7 in the Appendix, solutions of 10 percent nylon
concentration were originally prepared. However, these formulations
suffered from a disruption of the film surface similar to that encountered
with unmodified latices. An attempt to overcome this difficulty by
incorporating a viscosity modifier, Avibest, was partially successful.
However, the preferred approach was to increase the viscosity by raising
the polymer concentration to 25 percent. These formulations gave
generally satisfactory results. However, to prevent flotation during the
period before most of the low-density alcohol was leached out of the film,
it was necessary to add fairly high levels of fillers. Eventually, for
the tank experiment, the expensive Ti02 was satisfactorily replaced by
barytes.
The feasibility of this system has been established and its usefulness
will depend primarily on its comparative cost effectiveness and on the
evaluation of the possible environmental impact of the alcohol.
Hot Melt Materials
Hot melt compounds are essentially 100 percent solid materials which
become sufficiently fluid at elevated temperatures for application to
various substrates. Blends can be formulated to give various properties
as required by the end use. The primary advantage of hot melts is that
they eliminate the use of solvents during shipping and storage, thereby
reducing fire hazards and toxicity problems. The successful use of these
compounds depends largely upon a combination of properly formulated
materials and the development of suitable application equipment.
For the purpose of this program it was anticipated that the hot melt
would be extruded directly into water to form a barrier film. Furthermore,
24
-------
it was visualized that the melting of the compound would be accomplished
on board a surface craft and the melt pumped through a hose to an under-
water nozzle. Since a low-melting compound would reduce the complexity
of the equipment, it was decided early in the program that the hot melt
should have a low melting point (preferably in the 200 to 250 F range)
and a low viscosity. These requirements restricted the number of candidate
polymers to some extent.
Polymers
Hot melts can be considered as consisting of three major components as
shown in Figure 8. A number of elastomeric polymers whose properties
made them suitable candidates for this program are commercially available.
Among those selected for study were (a) ethylene/vinyl acetate (EVA),
(b) ethylene/ethyl aerylate (EEA), (c) ethylene/acrylic acid (EAA), and
(d) polycaprolactone (PCL).
Both EEA and EVA polymers showed promise as base resins for hot melt
films. EAA also showed promise. However, because of its high melt
viscosity and high cost, only a limited amount of work was done with it.
The ethylene copolymers are available'in a range of melt indices (MI)
which, in turn, is the weight of resin extruded per unit time under
standard temperature and pressure. Thus, a low MI indicates high melt
viscosity. Conversely, a high MI .shows a low melt viscosity. Work with
these copolymers indicated that within a given class of resins, superior
films could be obtained with those having a low melt index. However,
the higher melt viscosities would necessitate higher extrusion temperatures,
Polycaprolactone (PCL) formed strong, flexible films. Although the
melting point is low (60 C), its melt viscosity is high. As a result,
high temperatures were necessary for smooth castings. Attempts to reduce
melt viscosity by blending with modifying agents were not successful
due to incompatibility of the selected materials. Later it was noted that
the PCL films became quite brittle with age. Because of these factors,
work with this particular compound was discontinued.
Viscosity Depressants
Viscosity depressants help lower the viscosity and softening points of
hot melt blends. An extremely large number of these compounds are
commercially available. Those selected for study in this program were
hydrocarbon resins, mineral oil, and asphalt. The hydrocarbon resins
included vinyl toluene copolymers and low molecular weight polystyrenes.
The compound showing the most promise was Klyrvel, believed to be a
low-molecular-weight polystyrene. Based on a limited amount of work,
it appeared that up to half of the polymeric component could be replaced
with this resin without seriously affecting the properties.
25
-------
Polymer
Strength, flexibility, cohesiveness
Hot-melt
compound
Viscosity
depressant
Wetting,fluidity, plasticity
Waxes
Moisture resistance, cost reduction, fluidity
FIGURE 8. EFFECT OF COMPONENTS ON PROPERTIES OF
HOT-MELT COMPOUNDS
26
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Mineral oil, at 15 percent concentration, helped reduce melt viscosity
of EVA-based blends but also cuased a noticeable reduction in strength.
No further work was done with this material.
Only a limited study was made with asphalt compounds. The addition of
asphalt to EVA blends produced a very soft, tacky film. In addition,
wax did not appear to be compatible with this system.
Waxes
Waxes provide viscosity control for hot melts at elevated temperatures
and help reduce costs. Both paraffinic and microcrystalline waxes were
included in this study with the former showing the most promise. In
general, it was found that (1) up to 50 percent wax could be used without
seriously reducing strength properties, and (2) the lower melting point
waxes were superior to those with high melting points.
Hot Melt Blends
A large number of low-melting blends were evaluated for potential use
as barrier films. Criteria for use were low melting and low melt viscosity.
The results of tests on these experimental compositions are summarized
in Table A-l in the Appendix. Since physical requirements for these
materials have not been fully established, the data in the table are
qualitative and for comparing one composition against another. The
formulations and characteristics of two compounds showing the most promise
are listed in Table 1. Continuous films were prepared on the continuous
draw down roll using these two formulations.
These two blends were variously modified by the addition of (a) 10 parts
of sulfur, (b) 20 parts of zinc dust, and (c) 20 parts of barium sulfate.
These fillers were used, not only to increase the density of the films,
but also as possible mercury scavengers. Films of these compounds were
also successfully prepared on the continuous draw down apparatus.
Although the tear strength was somewhat reduced, the overall properties
appeared to be adequate for use as barrier films.
MATERIAL EVALUATION
Material evaluations consisted of dialysis experiments to measure
barrier effectiveness and microbiological-biological evaluation of the
candidate barriers.
Dialysis Experiments and Analytical Procedures
To measure effectiveness of the various plastic barriers in retaining
mercury, permeability measurements had been proposed with aqueous
27
-------
TABLE 1. CHARACTERISTICS OF SELECTED HOT MELT BLENDS
oo
Film Characteristics
Composition
Sample EVA
Number 505
28-3 25
29-1
DHv' Wax
6169 A-143
50
25 50
Klyrvel
60
25
25
Viscosity
Film
F cps Thickness, mils
202 8,800 8
201 20,800 8
Flexib-
ility
G
G
Crease
Resistance
G
G
Tear
Strength
F
F
Appear-
Drape ance
Medium Hazy
Medium Hazy
Raw Material
Costs, $
$0.28
$0.22
(a) Ethylena ethyl acrylate
-------
.solutions of inorganic and organic mercury compounds using known concentra-
tions. Some tests were also conducted later in the program with mercury-
contaminated sediments under aerobic and anaerobic conditions.
Dialysis cells were constructed of size 40 o-ring tubes having 4.2 inches
inside diameter (see Figure 9). The film samples of 13.8 cm2 effective
area were sealed with rubber gaskets of 1/8-inch diameter. The whole
assembly was held together by means of plexiglass plates which clamped
the opposite portions of the cell together and were fastened with screws
on the four corners of the plates- The bottom part of the cell was
closed off near enough to the film to permit strong agitation which was
obtained with a magnetic stirrer. A side arm permitted venting of any
air entrapped underneath the membrane and could also be used as an entry
port to remove samples, as the occasion arose.
The original goal of determining rate constants for the plastic films
had to be modified when it was shown early in the program that both
inorganic and organic mercury species were readily absorbed by the glass
and plastic surfaces with thich they came in contact.
As recommended by the Project Monitor, the analytical procedure adopted
throughout this program is based on flameless atomic absorption. The
method according to Storet No. 71900 and No. 71890 was followed. The
limit of detection achieved in aqueous samples was 0.2 M-Hg/1.
Problems were also encountered in the analysis of film samples for
mercury content. Since the recommended procedure did not disintegrate
most of the plastic films, there is no assurance that all of the mercury
in these films was detected. The main exception to this conclusion is
the nylon 6 film which completely dissolved in the nitric acid. The
hot melt compositions, although melted down during the digestion
procedure, remained in a separate, immiscible phase, and therefore, could
possibly have trapped some of the mercury content. With the exception of
the nylon 6 film, the analytical data for the mercury content of other
membranes are suspect and have generally not been used to derive
conclusions.
On the other hand, the analytical technique was able to detect mercury
levels in aqueous solutions down to a concentration of 0«2 p.gHg/1. The
most significant data from the dialysis runs, therefore, are the mercury
levels found on the distilled water side of the films, across from the
mercury test solutions. Barrier screening tests were conducted over
night for 15-hour periods and the solutions were analyzed the same day
the test was completed to minimize mercury absorption on the container
surfaces.
Preliminary screening tests with mercuric chloride (HgC^) solution
showed no detectible levels in the distilled water across the sample.
A long-term test was conducted, therefore, for a little over one week.
Again, as the data summarized in Table 2 indicate, no detectible transfer
of mercury across any of the films occurred. It should be noted that
the test with nylon 6 was run for 15 hours only. However, the HgCl2
level of the test solution was doubled to accelerate the dialysis.
29
-------
X
\
\
I O
•••••-
m
FIGURE 9. DIALYSIS-CELL APPARATUS
-------
TABLE 2.. TRANSMISSION OF INORGANIC AND ORGANIC MERCURY THROUGH POLYMERIC FILMS
Long Term Dialysis
(a)
Short Term Dialysis
(a)
HgCl2 Transmission^ HgClCH3 Transmission^ Hg(CH.j>2 Transmission^
Films
Generated In Situ
Hot Melt 35-1B
Elvamide 72-3
Preformed
Low Density Polyethlene
High Density Polyethylene
Polyvinyl chloride
Nylon 6
(a) Long term dialyses were
(b) Initial concentrations
Film
Thickness,
mils
8.5
21
4
2
4
2
carried out
P.gHg/-l
<0.2
<0.2
<0.2(c)
<0.2
<0.2
<0.2(d>
for one week;
of test solutions were 20
% of Test
Solution WgHg/£
..---- --
<1.5 0.44
<1.5 <0.2
<1.5 * 2.2
<1.5 , 0.4
<1.5 1.0
<0.75^ <0.2
short term dialyses were
ugHg/'t except where noted
% of Test
Solution HHg/-t-
3.3 1.2
< 1.5 0.22
16 0.8
3 0.32
7.4 0.32
< 1.5 <0.2
carried out for 15 hours.
otherwise; calculations of
7. of Test
Solution
9
1.6
6
2.4
2.4
<1.5
% Hg transmission
were based on the initial concentration.
(c) This test was conducted
(d) This test was conducted
for 4 days.
for 15 hours
with a test
solution of 40 ugHg/£ initial concentration.
-------
Shorter evaluations were also carried out with these same films using
methylmercuric chloride, (HgClCH3), and dimethyl mercury, [Hg(CH3>2],
solutions. Unlike the tests with the inorganic mercury, transfer of the
organic species was demonstrated in all but one of the films. In comparing
the data in Table 2, the reader is cautioned to take account of the
differences in thickness between the films. The preformed films were
evaluated at thicknesses that will most likely be employed in the field,
the differences generally depending on the commercial availability and
the physical strength of the barriers. The hot melt and Elvamide films,
which would be generated "in situ", were tested at greater thicknesses
than the preformed films, since the production of 2 to 4-mil films may
not be practical under water.
The most important conclusions that can be derived from the data in the
table are
(1) Nylon is the best barrier of all the films tested
both for inorganic and organic mercury compounds.
(2) High-density polyethylene is the next best barrier
material.
(3) Organic mercury compounds tend to pass through
most plastic films more rapidly than the inorganic
form.
Within the limits of these tests, a very good probability for success-
fully containing mercury in contaminated sediment seems to have been
demonstrated.
Some dialysis experiments with hot melt compositions incorporating such
potential mercury scavengers as sulfur or zinc were also carried out.
However, the results remained inconclusive because of the difficulties
encountered in analyzing polymeric films. Mercury absorption data for
several of the membranes such as polyvinyl chloride, low density poly-
ethylene, and hot melt compositions strongly suggest that mercury
absorption may be a feasible alternative to containment, should this ever
become the preferred procedure.
Some dialysis runs were also undertaken with hot melt films employing
mercury contaminated sediment as the dialysis medium. A strongly
contaminated sediment was obtained for this purpose and was slurried to
a fluid condition with 10 parts distilled water. One portion of this
slurry was aerated with oxygen over night, and the other one was refluxed
for the same period to drive off gases. The mercury content of the
oxygenated sample was 29 ppm and that of the boiled sample was 23 ppm.
The difference may be considered to reflect the loss of volatile mercury
compounds. The mercury was present largely in water-soluble form as
indicated by a mercury content of the supernatant liquid of the original
sediment of 17=3 mg/1. Mercury transfer from the oxygenated mud through
the hot melt film was 0.11 M-gHg and from the boiled mud 0.03 u-gHg. This
reinforces the conclusion that a volatile, probably organic, form of
32
-------
mercury was lost from the boiled sample, and that this form preferentially
permeated the hydrocarbon film. From the information in Table 2, it may
be inferred that a nylon film would most probably have contained the
mercury in the sediment.
BOD Experiments
Three types of laboratory and one field evaluation were undertaken on
seven candidate barrier polymers. Biochemical oxygen demand (BOD),
bacterial growth in water containing leached polymer specimens, and
associated evaluations on polymer leach water (dissolved oxygen or DO,
total carbon or TC, and pH) were conducted to determine whether there
might be adverse environmental effects in waters where the barrier films
are applied. Laboratory evaluation against fungi and freshwater
exposure to bottom organisms were initiated to allow an estimation of
whether the films are resistant to fungal or invertebrate degradation
and will therefore have a reasonable period of performance. Specimens
of the polymers were cut to appropriate sizes as follows:
Leaching - 5 x 10 cm (also used in bacteriological study)
Fungal Study - 5 x 5 cm
Field Study - 7 x 7 cm
At least three replicates were prepared for each type of specimen.
The leaching water used was the PAAP medium (see reference 3 in Section
VII). This is a balanced minimal salts medium containing a total of
85.7 mg/1 of mineral salts. Distilled-deionized water of high purity
(1 x 10 ohms cm) was used in preparing this medium.
The BOD procedure was the one outlined in Standard Methods (see reference
4 in Section VII) except that a special electrode (YS Instrument Company,
self-stirring BOD bottle probe) was used to measure DO. A radiometer pH
meter with pencil electrode was used to measure pH, and a Beckman Infrared
Carbon Analyzer was used to measure total carbon (TC).
The bacteriological study consisted simply of replacing leach water
(removed for BOD and other evaluations) with equal amounts of water
medium, inoculating with sewage seed at essentially the rate employed
for BOD (0.1 ml/100 ml), and estimating initial and final (48 hr) cell
numbers by standard petri plate counting procedure,,
The petri plate procedure for the fungal evaluation is described in
CCC-T-191b (see reference 5 in Section VII) with the inclusion of an
additional nutrient medium to compare with the non-nutrient mineral
salts agar medium (MSA). Spray inoculation (approximately 0«4 ml of an
inoculum containing 2 x 10^ fungal spores per ml) of polymer specimens
was accomplished with a No. 82 Devilbiss atomizer. The 7 day fungal
cultures used in preparing the inoculum were Aspergillus niger, A.
33
-------
tLerreus, Chaetomium globosum, and Peniclllium citrinium. Stock cultures
were maintained on PDA test tube slants. The inoculated specimens were
incubated at 25 C and observed for fungal growth after one week.
Exposure of the seven polymers to freshwater bottom organisms was
accomplished by means of Hester-Dendy multiple plate samplers (see
reference 6 in Section VII), The samplers were composed of 7 x 7 cm
masonite plates mounted alternately with 2.5 x 2.5 cm masonite spacers
on 10 cm stainless steel eyebolts and held tightly in place by means of
stainless steel nuts. Duplicate polymer specimens (7x7 cm) with a
center hole to fit the eyebolt were placed on either side of seven
spacers with plates on both sides of the specimens. Four sets of samplers
were then placed in shallow water (approximately 4 feet depth) in Battelle's
research lake. One sampler was to be removed after two weeks, and others
after one, two, and four months of exposure. The results of these
studies to date are presented in Table 3.
The following comments on polymer performance can be made.
(1) On the basis of minimal changes in pH, DO, and BOD,
and limited TC addition to the leach water, the
polyethelene, hot melt, and PVC polymers appear to
be most promising candidates. However, all may be
susceptible to attack by fungi, and components of
the hot melt polymers supported increased bacterial
growth after initial leaching. Data on bottom
organism attachment and growth are not conclusive
at this time.
(2) Keltex (alginate) disintegrated after short periods
of time in water, drastically lowered pH, and
contributed significant TC to leach water. For
these reasons, this polymer cannot be considered
for extended bottom life application.
(3) The negative results obtained with alcohol soluble
nylon film prepared "in situ" in which the polymer
made a high TC contribution to leach water (see
results for alcohol soluble nylon solution), are a
reflection of the beaker scale experiment; at much
greater dilution in a lake, the effects may be
negligible. The difference in TC and BOD values for
alcohol soluble nylon solution (5575.0 mg/1 and
6.1-7.2 mg/1, respectively) may indicate that the
leached-out components of this polymer are toxic or
at least not fully utilizable by the sewage seed
bacteria at the concentration prevailing in the
experiment.
Although slight colonization of organisms including snails, oligochaeia,
and larvae of odonate and diptons on masonite plates in the Hester-Dendy
samplers was observed after two weeks of exposure, no organisms had
34
-------
TABLE 3. RESULTS OF MICROBIOLOGICAL AND RELATED STUDIES OF POLYMER BARRIERS
Leachflte
_ . , Initial Dissolved _. . . , „ Bacteria
Total Biochemical Oxygen
Carbon Oxygen, mg/£. *• ' Demand, me AC,. i>rowcn.
Code Designation
Blank
High density polyethylene
Preformed low-density
polyethylene
34-1 (hot melt composition)
35-1 (hot melt composition)
27. Keltex (alginate)
Nylon film
Alcohol soluble nylon solution
Polyvinyl chloride
Filter paper
PH
7.1
7.4
7.0
7.3
7.2
3.5
6.4
6.7
7.1
--
ms/i. Undiluted
8.82 x 10
cells/rat).
(d) -= no visible fungal growth on specimen, ±= slight growth, -H= moderate growth, and -H-= profuse growth covering
.entire specimen.
(e) Only slight bottom organism activity to date. Evaluation continuing.
(f) Sample diluted 1:100 because of high TC (values corrected for dilution).
(g) Bacterial growth (and oxygen utilization) were apparently limited by low pH or soluble polymer toxicants.
(h) Completely disintegrated.
-------
attached to the polymer specimens. Keltex (alginate) had disintegrated
during the two week exposure period.
EQUIPMENT EXPERIMENTS
Experiments were carried out with most of the material systems as they
were developed in the laboratory. The primary means of evaluation was
with a small scale test tank into which overlay of one or two feet in
width can be deployed. The tank is 18 feet long, 3 feet wide, and 20
inches deep. Rails are installed at the top edge of the tank so that a
carriage which holds test apparatus and experimental dispensing means
can be moved along the length of the tank. In addition to this apparatus,
The Battelle Ocean Research pool and a Columbus Recreation Department
swimming pool were used for large scale evaluations of preformed film
experiments.
Experimental equipment was developed and experiments were conducted
throughout the program with all of the candidate material systems.
Equipment for Coagulable Materials
A one-foot-wide nozzle was designed and constructed for experiments with
coagulable materials. Polymer was supplied to the nozzle with a positive
displacement rotary screw pump and acid solution or other gelling agents
were supplied by a self-priming flexible impeller pump. Supply tanks
and pumps are mounted on the carriage which fits on the test tank.
Figure 10 shows how this apparatus is arranged on the test tank.
The nozzle is designed so that the polymer and gelling agent can be co-
extruded into the water. Figure 11 is a schematic cross section through
the nozzle which shows this relationship. The polymer exit and the top
gelling agent exit is shown in Figure 12, a photo of the exterior of the
nozzle.
The design of the one-foot-wide nozzle is very similar to that used for
producing polymer film in a program for the Supervisor of Salvage, U.S.
Navy, several years ago.
The initial experiments with the one-foot-wide nozzle were made with
sodium alginate polymer and a 10 percent HCl solution gelling agent.
Satisfactory results were obtained, and experiments proceeded with other
coagulable materials.
Coagulable Latex Compositions
At the very beginning of this research, an experiment was conducted with
a coagulable carboxylated 50/50 butadiene-styrene copolymer. This
36
-------
,
-
U3
)
FIGURE 10. TEST TANK AND TYPICAL APPARATUS
-------
00
POLYMER
GELLING
AGENT
POLYMER EXITS^
•'::'K-;^:\^^^^'^'-.:^:li^;Si!^^- ' ' — ""> -k —
WsW^xZ^^ G t
^_ GELLING AGENT EXITS
ELLING AGENT EXITS
DIRECTION OF MOTION
FIGURE 11. SCHEMATIC CROSS SECTION COAGULABLE POLYMER NOZZLE
-------
FIGURE 12. EXTERIOR OF EXPERIMENTAL COAGULABLE
FILM NOZZLE
FIGURE 13. FR-S-257.BASED LATEX EMERGING FROM
EXPERIMENTAL NOZZLE
39
-------
consisted of latex (FR-S 257) 80 percent, Superloid (2 percent aqueous
solution) 17 percent, and TiC>2 4 percent. Although a smooth coherent
polymer layer was extruded from the nozzle, only a thin skin formed on
the latex layer, which broke up as the material settled into the bottom
of the tank. Figure 13 shows the latex film emerging from the nozzle.
The water in the tank was not disturbed and no further coagulation of
the latex compound occurred.
It seemed apparent that the gelling agent was not in contact with the
polymer long enough and in great enough concentration to effect coagulation.
The laboratory experiments had produced an exceptionally tough, solid,
pliable film, but this had apparently resulted from the relatively long
exposure to the HCl in the tray.
This first experiment was followed by a trial run with a similar latex
system. This consisted of latex (FR-S 257 69.4 percent, Superloid (2
percent aqueous solution) 13.9 percent, TiC>2 16.9 percent. The previous
experiment had been conducted with a nozzle opening of 0.125 inch; this
experiment was carried out at 0.035-inch nozzle opening. It was reasoned
that a thinner polymer film would effectively increase the HCl-to-polymer
ratio, and that this would result in a stronger film. Unfortunately,
unsatisfactory results were again obtained; that is, skin coagulation and
film breakup.
Because of the above results, additional laboratory experiments were
conducted in a manner intended to simulate the dilution of gelling agent
experienced in the tank experiments. Latex films drawn down on glass
plates were momentarily dipped into gelling agent and then immediately
immersed in fresh water. It appeared from these simple experiments that
5 or 6 seconds of exposure to the HCl solution was required for most
latex systems to cause sufficient coagulation to obtain a coherent film.
Although only one side of the film was exposed to the gelling agent, the
film thickness of the total cast film was only about 20 mils, or half of
that in the tank experiments. These laboratory experiments could only
approximate tank conditions but they did show that a minimum time is
required to obtain coagulation with these particular rubber latices.
Laboratory work was directed toward reducing the gellation time of the
polymer. Another experiment was conducted with a polyvinylidene chloride
based latex, consisting of latex (Daran 220) 77-1/2 percent, Santicizer
E-15 7 percent, Superloid (2 percent aqueous solution) 15-1/2 percent. A
20 percent HCl solution was used for gelling agent. The nozzle opening
was set at 0.030-inch. Although bench scale experiments had indicated
that a tough film could be formed with HCl, the results of the experiment
were unsatisfactory with the production of only shards of coagulated
latex and considerable dispersion into the water.
This experiment was followed immediately with another one using the same
polymer and a 40 percent AL£ (80^)3 solution as coagulation medium. A
nozzle slit width of 0.030 inch was also used in this experiment. A
substantially whole film was produced but a few inches from the nozzle
the film broke and settled to the bottom of the tank. Figure 14 shows
40
-------
FIGURE 14. DURAN 220-BASED LATEX EMERGING FROM
EXPERIMENTAL NOZZLE
FIGURE 15. ALCOHOL-SOLUBLE NYLON EMERGING FROM
EXPERIMENTAL NOZZLE
41
-------
this material as it emerged from the nozzle. Note the fracture of the
film a few inches from the exit. No dispersion of the polymer into the
water in the tank was observed. It was noticed during this experiment
that the gelling agent was not impinging on the polymer smoothly as it
was co-extruded from the nozzle.
Modifications of the apparatus to incorporate shrouding which would
increase the contact time of the polymer and gelling agent was considered
as a possible next step. Concurrent with the work on latex-based coagulable
polymers, considerable success was being achieved with simpler alterna-
tive approaches. In view of the additional complexities of the latex
systems, further work on these materials was terminated.
Alcohol Soluble Nylon Films
The nylon/alcohol system is described earlier in this report. The basic
film-forming phenomenon is based on the fact that water is a nonsolvent
for the resin and the alcohol is water-miscible. Diffusion of alcohol
out of the film and of water into the film structure produces the solid
barrier.
Our experiment was conducted in the test tank at the end of the program.
The apparatus was simply a slit nozzle through which the nylon/alcohol
solution was extruded into the water. Although the film was somewhat
nonuniform and thick because of poor extrusion, a continuous, coherent,
and very tough film was formed in the tank. Figure 15 shows the alcohol
soluble nylon emerging from the nozzle and Figure 16 shows the resulting
film on the tank bottom after the water had been drained from the tank.
It is believed that the large unbroken bubbles in the film are caused by
nonuniform flow of the polymer which produced thin spots in the film
solution as it was extruded from the nozzle.
Because this experiment appeared to show that this general approach was
feasible, no further equipment modifications were conducted.
Hot Melt Film Experiments^
Experiments were conducted with three different approaches to producing
a film of hot melt material.
Direct Extrusion
It was originally thought that hot melt materials could be formed by direct
extrusion into the water. A steam jacketed nozzle was designed and
constructed that could be suspended from the carriage on the 18-foot
long test tank. Figure 17 shows an exterior view of the nozzle and
Figure 18a shows a schematic sketch of its cross section. Molten hot melt
material is supplied from a heating kettle by a positive displacement
rotary screw pump.
42
-------
FIGURE 16. COAGULATED NYLON FILM FORMED IN TEST TANK
FIGURE 17. HOT-MELT DIRECT EXTRUSION NOZZLE
V!
-------
Molten hot-melt compound
• Steam
Solid film
Y////////////
a. Direct Extrusion Method
Molten hot- melt compound
Steam jacket
Air
Air chamber
Solid film
b. Curtain Coat Method
-Molten hot-melt compound
-Air
Draw bar
Air chamber
Teflon-coated drum
Solid film
Direction of Motion
c. Continuous Draw-Down Method
FIGURE 18. HOT-MELT-COMPOUND EQUIPMENT APPROACHES
44
-------
It was decided to use tuffin 30, a 30/70 copolymer of ethylene and
vinyl acetate and paraffin wax in the experiments with this apparatus.
This composition was used because a large supply was on hand and its
fairly low viscosity and low melting point of 200 F made it ideal for
handling. In our experiments with the hot melt material and the direct
extrusion approach, considerable difficulty was encountered in keeping
the hot melt from adhering to the lips of the nozzle; this prevented
the formation of a coherent film. A large quantity of film was produced
in our experiments, but most of this material was unacceptable because
of the longitudinal discontinuities caused by this problem. Additionally
much hand work was required in the tank to prevent the nozzle from clogging
completely. A number of solutions to the problem were tried in our attempt
to improve nozzle performance. Moderate success was obtained with
Teflon-coated nozzle parts to reduce the tendency of the hot melt
material to adhere to the nozzle. However, it appeared that some type
of additional heating would be necessary at the nozzle exit to keep the
hot melt material from solidifying. Three possible approaches are:
(1) use a hot-water film co-extruded above and below the hot melt,
(2) provide a steam passage at the extreme exit of the nozzle, and
(3) use both methods in combination to achieve the desired results.
Because these approaches required a completely new nozzle with at least
seven different chambers for water, steam, and hot melt material, it was
decided to defer this proposed approach temporarily and investigate
another hot melt compound.dispensing concept which was basically different
but could use the existing nozzle.
Curtain Coat Method
The sketch in Figure 18b shows an approach for handling the production
of hot melt films where the water is not in contact with the nozzle.
Because the hot melt nozzle outlet does not contact the water, the hot
melt compound remains molten until it strikes the water. This setup
was simulated in the laboratory by mounting the nozzle vertically above
the water in the test tank without the air bubble chamber. It was
possible to obtain a large quantity of continuous film in this manner.
An appreciable variation of thickness was noted in both the longitudinal
and transverse sections of the film. However, the obvious cause of this
condition was a variation in the rate at which the chilled film was
removed from the surface of the water. Small bubble holes also appeared
in the film which were probably a result of entrapped water vapor from
leaks between the hot melt chamber and the steam jacket. Nevertheless,
this experiment was the first in which a quantity of substantially whole
film was made with the hot melt material.
Continuous Draw Bar Method
Consideration of the problems in this approach leads one back to the
method used in bench-scale experiments to produce hot melt film samples;
that is, a draw bar. The molten material is drawn down against a
surface and produces uniform thin films. The apparatus in Figure 18c
45
-------
shows how continuous film forming may be accomplished based on this method,
Molten hot melt material is fed to a trough formed by the curve of a
moving Teflon-coated drum and a draw bar. The film is chilled on the
bottom side by contact with the drum and on the other side when it
contacts the water. Film is stripped off the bottom of the drum.
It was decided to fabricate a bench scale model of this apparatus which
would produce hot melt film about 6 inches wide. Figure 19 shows this
apparatus with the draw bar positioned at about 15 degrees down from the
vertical. The small plastic pan provides the cooling water and the
squeeze blade mounted against the drum prevents droplets of water from
prematurely chilling the hot melt material as it is poured behind the
draw bar.
Continuous lengths of hot melt film of up to 100 feet long, in thick-
ness of 0.006 to 0.014 inches have been made. Figure 20 shows film
being produced on the apparatus. The length of film that can be
produced appears to be limited only by the supply of hot melt material.
Every experimental run with filled and unfilled hot material was success-
ful. The only shortcoming appears to be a mild longitudinal serration
which apparently is caused by a chilling of small particles adhering to
the exit edge of the draw bar.
Heating of the draw bar—perhaps with an electric heater—should eliminate
this problem or a heated "pressure" roll could be used following the
draw bar.
Preformed Film Experiments
The films which are expected to be formed from either the hot melt
compounds or from the coagulable polymers are solid, flexible, and rather
strong. These physical characteristics appear to be necessary for long
life and good barrier properties. When the application apparatus of
these films is visualized, there is a striking similarity to an apparatus
system which dispenses preformed film from a roll. The physical character
of the films which have been developed so far is not unlike common
preformed films which are made in large commercial quantities. Therefore,
it appeared prudent to look at the problems of handling preformed film
under water in the test tank so that problems with the candidate film
material systems could be anticipated, and because preformed films could
conceivably produce barrier properties superior to "in situ" processes
at a lower cost.
The first experiments were conducted to show that preformed films can be
deployed under water to cover the bottom. To accomplish this result,
several conditions must be met:
• The material plus weights must have a specific
gravity greater than 1.0.
• Weights must be placed in such a manner as to
stabilize and keep the film down.
46
-------
-
FIGURE 19. ARRANGEMENT OF CONTINUOUS DRAW-DOWN APPARATUS
FIGURE 20. CONTINUOUS DRAW-DOWN APPARATUS IN OPERATION
47
-------
• The material must have sufficient thickness or
stiffness to prevent wrinkling and folding.
Good results were obtained using 0.004 low-density polyethylene with
concentrated weights attached in a pattern over the film surface. We
did attempt to use 0.001 Saran which has a higher specific gravity than
polyethylene, but this material was too limp to be successfully laid in
the tank bottom in a whole piece. A number of experiments were conducted
involving the placement of weight on polyethylene film and its subsequent
application to the bottom of the test tank. A summary of these experiments
is shown in Table 4.
The experiments demonstrated the feasibility of fabricating a preformed
film and applying it to the bottom. Another experiment was planned to
demonstrate the application of preformed film. In this experiment a
10-foot-wide by 85-foot-long preformed polyethylene sheet was prepared
with concentrated weights in a 2.8-foot by 2.8-foot matrix. The anchors
averaged 0.021 pound per square foot. The film was rolled onto a 6-inch-
diameter core and bright stripes were painted on its surface for visibility.
This film was very successfully deployed to the full length of a 75-foot
long, indoor swimming pool. After initial deployment the film was rerolled
underwater onto the core. The film was subsequently unrolled and rerolled
two additional times. Figure 21 shows the film in various stages of
deployment.
Based on this very successful experiment, more data on preformed film was
obtained and dialysis experiments were conducted with typical commercially
available materials.
ANALYSIS OF IMPLEMENTATION COSTS
The only practical means for generating an understanding of the cost of
implementation of these candidate systems is to generate a possible
mission profile and apply incremental cost estimates to each of the
elements which have been identified as part of the system to be implemented,
Obviously, since the work that has been done so far has been accomplished
on a laboratory scale, and specific quotations have not been obtained,
the cost estimates are credible primarily in a comparative sense. Hope-
fully this initial effort can serve as a worksheet which can be improved
and revised as more concrete cost data are obtained. The cost analysis
consists of estimates for several elements of the overall costs for the
three material/equipment systems identified in this program. Thus costs
have been estimated for material, predeployment operations, deployment
operations and equipment for systems which utilize preformed film, a
nylon/alcohol coagulable polymer, and hot melt materials.
Cost of Materials
The cost of the basic materials is based on a number of considerations
48
-------
TABLE 4. SUMMARY OF PREFORMED FILM EXPERIMENTS
Film Material
Anchor
Anchor Placement
Comments
Polyethylene
2' x 10'
x 0.004
Polyethylene
2' x 10'
x 0.004
Polyethylene
I1 x 12'
x.0.004
Polyethylene
1' x 12'
x 0.004
Polyethylene
2' x 6'
x 0.004
Polyethylene
I1 x 12'
x 0.004
Saran
I1 x 20'
x 0.001
Polyethylene
2' x 10'
x 0.004
Polyethylene
2' x 10'
x 0.004
Polyethylene
4f x 3'
x 0.004
Polyethylene
2' x 20'
x 0.004
Polyethylene
10' x 85'
x 0.004
Sand
Sand
Sand
Sand
Sand
Metal Rods
1/8"
None
Loose placed.
Glued all over.
Glued in strips.
Glued in buttons or
lumps over surface.
Contained in heat
sealed tubes.
Woven across trans-
verse direction
6" cntr's.
N.A.
Metal discs Glued in I1 x I1
matrix
0.28
Metal discs Glued in 1.5' x 1.5'
matrix
0.16 £/ft2
Metal discs Glued in 2.8' x 2.8"
matrix
0.018 #/ft2
Metal discs Glued in 1.5' x 1.5'
matrix
0.16 #/£t
Metal Discs Taped on 2.8' x 2.8'
matrix „
0.018
Polyethylene floated out from
under the sand and sand ran
to low spots, (tank)
Polyethylene stayed down but
became stiff due to the rubber
base glue, (tank)
More flexible, stayed down but
wanted to float between,
rubber base glue, (tank)
Stayed down and conformed
rather well, epoxy bond came
off after immersion, (tank)
Somewhat stiff in transverse
direction perhaps somewhat
expens ive. (tank)
Very stiff in transverse direc-
tion, (tank)
Conformed reasonably well but
had tendency to bunch in
transverse direction, (tank)
Good conformation to bottom.
(tank)
Good conformation to bottom.
(tank)
Good conformation to bottom.
(Placed at 12' depth in
research pool)
Good conformation to bottom.
Used in 18' x 3' test tank
and 25' x 15' x 12' research
pool.
Very good results when unrolled
to 75' length in swimming
pool.
49
-------
;,
FIGURE 21. VIEWS OF LARGE-SCALE PREFORMED FILM EXPERIMENTS
-------
including, strength, in-place thickness required, method of fabrication,
and means for anchoring the film.
Basic Material Costs
The costs of materials shown in Table 5 were based on the best information
available at this time. Specific gravity of some of the blends could
vary, and since quotes were not obtained and the effect of quantity
purchases was not determined, the cost could vary somewhat from that
shown. It is believed, however, that the tables reflect a reasonable
comparison of cost.
In addition to basic material and anchor weighting cost, a conversion
cost is incurred with each of the candidate systems to prepare the
material for deployment -
A nominal width of 20 feet has been selected as the width of overlay to
be deployed. Preformed polyethylene film can be obtained in this width,
but standard material is supplied in a gusset fold of only about 100 to
300 feet in length. It will be necessary, therefore, to unroll and unfold
the film and reroll it on large cores 20 feet or more in length. Because
more than 100 to 300-foot lengths are to be deployed, a transverse seam
must also be made. Nylon, PVC, and high-density polyethylene films are
available in five to seven foot widths. Therefore, continuous longitudinal
seams will be necessary with these materials. It is not expected that
additional labor cost will be incurred with the longitudinal seams how-
ever, and that the conversion operation could probably be accomplished at
60 feet per minute using 2 men or about $0.0003 per square foot.
Conversion costs for the nylon/alcohol and the hot melt systems involve
the combination of the constituants. Nylon/alcohol will require a
heated kettle with an agitator and a reflux condenser. One hundred
gallon kettles are common and one man can probably handle a batch of
500 pounds which would be about 60 gallons of solution. Mixing and
pumping into drums is estimated at 2 hours for a cost of $0.00250 per
square foot. Hot melt materials will probably require a somewhat longer
period of processing, say 2 hours, and another man will be needed to
extrude, chill and pack the material after it has been melted and combined.
Assuming a 500 pound batch again, the cost would bt $0.0050 per square
foot.
Anchoring Cost
The next cost to be considered is that of anchor materials. In previous
sections of the report, three anchoring systems were described: (1) pre-
fabricated attachment (only applied to preformed films), (2) screw-in
anchors, and (3) gravel ballasting. Table 6 summarizes the estimated
cost of these materials.
51
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TABLE 5. ESTIMATED BASIC MATERIAL COST
FOR POLYMER OVERLAY
Ln
Ma teria 1 /Equipment
System
Preformed Nylon
Preformed Polyethelene (H.D.)
Preformed Polyethelene (L.D.)
Preformed PVC
Alcohol-Soluble Nylon
Hot Melt (EVA base)
Hot Melt (EEA base)
* Includes conversion cost to
** Battelle estimate based on
Specific
Gravity
1.14
0.95
0.91
1.25
1.05
1.05
1.05
sheet where
knowledge of
Base*
Material
Cost,
$ /pound
1.80
ft. 35**
0.25
0.42
0.40
0.24
0.19
appropriate.
process.
Deployed
Film
Thickness ,
inches
.002
.002
.004
.004
.012
.008
.008
Pre-Deployment
Conversion Cost,
$ /square foot
.0003
.0003
.0003
.0003
.0025
.0050
.0050
Total Cost,
$/square foot
.0216
.0037
.0050
.0112
.0288
.0155
.0133
-------
TABLE 6. ESTIMATED COST OF ANCHORING POLYMER OVERLAY
Anchoring Method
Material
Equipment
System
Cost/
pound,
dollars
Weight/
square feet,
pounds
Cost/
square feet,
dollars
Prefabricated
attachment*
All preformed
films
0.090 0.018 0.00162* material
0.00139 attachment
cost
Screw-in anchors
Ballasting
(a) Preformed
(b) Hot melt 0.090 0.018
All systems 0.016 1.25
0.0030
0.0016
0.0020
* Although attachment of anchors in a prefabrication process could be
considered with conversion costs, it has been included here to be more
nearly comparative to the other "in situ" anchoring means.
Table 7 summarizes all of the predeployment costs (material, conversion,
anchor).
Deployment Costs
The cost of actual deployment depends to a large extent on the specific
site where the overlay will be used. Some of the factors are:
(1) Distance from land base
(2) Depth of water
(3) Weather conditions
(4) Bottom conditions
(5) Current
(6) Configuration of site.
Sample Calculations
Let us assume the following site for purposes of sample calculations:
• Site location - 50 miles from nearest land base (port)
• Site size - 20 acres (rectangular)
53
-------
TABLE 7. ESTIMATED COST MATRIX, MATERIAL/PREDEPLOYMENT
Ul
-p-
Total Predeployment Cost, $ /square feet
Material/Equipment System
Preformed Nylon
Preformed Polyethelene (H.D.)
Preformed Polyethelene (L.D.)
Preformed PVC
Alcohol-Soluble Nylon
Hot Melt (EVA base)
Hot Melt (EEA base)
Total Basic
Material Cost,
$ /square feet
0.0216
0.0037
0.0050
0.0112
0.0288
0.0155
0.0133
Prefabricated
Anchoring,
$0.0030/
square feet
0.0246
0.0067
0.0080
0.0142
NA
NA
NA
Screw-in In Situ
Anchoring,
$0.0016/
square feet
0.0232
0.0053
0.0066
0.0128
NA
0.0171
0.0149
Gravel Ballast
Anchoring,
$0.0020/
square feet
0.0236
0.0057
0.0070
0.0132
0.0308
0.0175
0.0153
-------
• Water depth - 25 feet
• Weather, bottom, and current - favorable.
Any of several equipment methods could be used, but a vessel and a barge
(for barge mounted equipment) and crewmen/workmen will be required. This
is estimated as follows:
Vessel 60 feet - $75/hour
Barge 80 x 40 feet - $25/hour
Crew of vessel - $20/hour/each.
Crew requirement should include 2 men for the vessel and at least 4 more
men for overlay operations. A schedule of events and the resulting costs
have been summarized in Table 8 for this mission.
Equipment Costs
Surface and subsurface equipment will be required to deploy the polymer
film. As was shown in the sections of this report describing equipment,
a barge mounted apparatus based on a commercial power crane-backhoe is
being considered as the primary handling unit. This apparatus will have
the subsurface polymer dispensing equipment mounted on the end of its
boom.
It is estimated that the basic crane-backhoe hardware will cost $45,000
for the preformed film ahd hot melt approach and about $35,000 for the
alcohol/nylon coagulable system based on the relative weight and bulk
of the apparatus.
The cost of actual subsurface equipment for each of the candidate systems
can only be a very preliminary estimate. However, the complexity of the
apparatus is reflected in the comparative cost figures.
Summary cost estimates of the equipment are shown in Table 9 which follows,
55
-------
TABLE 8. DEPLOYMENT COST SUMMARY
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Activity
Make ready
Start up
To site
On site preparation
and survey
Deploy film*
Crew boat, etc.
Secure equipment and
evaluate overlay
Return
Secure on shore
Secure equipment
TOTAL DEPLOYMENT COST
Crew
Requirement
4
2
2
4
6
4
6
2
2
4
Time,
hours
8
1
7
8
10
3
6
7
1
8
Crew
Cost,
dollars
640
40
280
640
1,200
240
720
280
40
640
Vessel**
Cost,
dollars
200
100
700
800
1,000
300
600
700
100
200
Total
Cost,
dollars
'840
140
980
1,440
2,200
540
1,320
980
140
840
$9,420
Sample calculations for various material/equipment concepts.
Polyethelene Preform (H.D.) 920,000 x $ .0053*** = $4,870 4- $9,420 - $14,290
920,000 x $ .0232 = $21,380 -f $9,420 = $30,800
920,000 x $ .0308 = $28,300 + $9,420 = $37,720
920,000 x $ .0149 - $13,700 + $9,420 - $23,120
Nylon Preform
Alcohol/nylon
Hot Melt
Thus, cost per square foot:
Polyethelene Preform (H.D.)
Nylon Preform
Alcohol/nylon
Hot Melt
$14,290/920,000 = $ ,0155/square foot
$30,800/920,000 - $ .0335/square foot
$37,720/920,000 - $ ,0410/square foot
$23,120/920,000 = $ -0251/square foot
* 10 rolls of .004 mill film at 100,000 to cover 46,000 x 20 acres - 920,000.
square foot
** Includes workboat, barge, and crew boat as appropriate.
*** See Table 7.
56
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TABLE 9. SUMMARY OF SURFACE AND SUBSURFACE EQUIPMENT
COSTS FOR A SELECTED MISSION
Estimated Cost,
Equipment Requirements dollars
I. Preformed Film System
1. Crane-backhoe unit 45,000
2. Subsurface equipment
(a) Dispenser, foot roll, etc. 40,000
(b) Underwater TV, etc. 2,000
3. Surface deck equipment
(a) Auxiliary power 3,000
(b) Deck handling 2,500
(c) Roll stands, etc. 2,500
Subtotal 95,000
II. Hot Melt Film System
1. Crane-backhoe unit 45,000
2. Subsurface equipment
(a) Dispenser, foot roll, etc. 75,000
(b) Underwater TV, etc. 2,000
3. Surface deck equipment
(a) Auxiliary power 5,000
(b) Hot melt pump 5,000
(c) Deck handling, etc. 3,000
(d) Gas fired kettle 2,500
Subtotal 137,500
III. Alcohol/Nylon System
1. Crane-backhoe unit 35,000
2. Subsurface equipment
(a) Dispenser 30,000
(b) Underwater TV 2,000
3. Surface equipment
(a) Auxiliary power and pumps 10,000
(b) Deck handling, etc. 2,000
(c) Vat and pumps 1,000
Subtotal 80,000
57
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SECTION VI
IMPLEMENTATION OF RECOMMENDED APPROACH
As evidenced by the results described in the report, the concept of a
polymer film barrier to contain mercury contaminants appears to be very
promising. Accordingly, the next logical step is a field test to
demonstrate the validity of this conclusion. A detailed description of
such a demonstration program has previously been submitted to the EPA
for consideration.
The program should be a carefully controlled experiment designed to
evaluate the effectiveness of polymer films in reducing or eliminating
the transfer of mercury into important lake biota. This work must
confirm the validity of both the material performance and the concept of
equipment used to deposit the film. Successful implementation of the
recommended program will depend to a great degree on careful planning
of the experiment followed by its execution.
Obviously, such a program will not be easy to implement, as many problems
will have to be solved. Therefore, the program proposed by Battelle
consists of 8 separate but related tasks planned to be executed in
an efficient manner to assure a successful program. These tasks are
summarized below.
Task I - Establish Program Plan - This task can be regarded
as the most important part of the entire program. The success
of the total effort will depend on the imagination, ingenuity,
and breadth of this task, since it must shape the entire
effort. The planning will determine how to treat the lake
bottom (site), and how to evaluate the effectiveness of the
treatment. Survey methods and experiments will be specified
and analytical procedures identified. Precautions must be
taken that no additional mercury is added to the site after
treatment of the bottom.
Task II - Pretreatment Site Survey - Data on the levels of
contamination at the site before treatment will be firmly
established within the limits prescribed by the experimental
plan.
Task III - Polymer Optimization - The polymer film composition
will be optimized to provide the best balance of handling
characteristics, barrier properties, strength, and cost.
Task IV - Equipment Design - Procedures and equipment to
dispense the film, adapted to the site conditions, will be
developed within the cost and time framework of the program.
59
-------
Task V - Site Treatment - The site will be treated with the
polymer film.
Task VI - Post Treatment Site Survey - The site will be
monitored according to the procedures and schedules established
by the work plan.
Task VII - Develop Plan for Large Scale Implementation - Based
on the results of Phase II, concepts and plans will be devised
for large scale use of polymer films for mercury containment.
Task VIII - Technical Support Activities - The value of the
demonstration can be enhanced to a considerable degree by
maintaining a constant, but low rate of effort, study of
polymer-mercury interactions. Of particular interest are
the effect of polymer structure (crystallinity, etc.) and
film orientation on mercury abosrption and permeability.
All of the above tasks are necessary to insure a successful program.
Battelle-Columbus has the personnel and facilities to assume responsibility
for.the total management of Phase II; that is, direct participation in all
8 tasks under the supervision of an appropriate EPA project officer.
The demonstration site must be selected and some of the operating problems
peculiar to the site identified before a cost proposal can be submitted.
60
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ACKNOWLEDGMENTS
The support of the project by the Environmental Protection Agency, and
specifically the help provided by the Project Officer, Dr. William R.
Duffer, and Dr. Curtis C. Harlin, Jr., both of the Robert S. Kerr Water
Laboratory, Ada, Oklahoma, and Mr. Charles E. Myers of the EPA, is
acknowledged with sincere thanks. We would also like to thank Mr. James
F. Shea of the Division of Engineering, Ohio Department of Health, and
Dr. John Konrad, and Mr. Larry L. Maltbey of the Wisconsin Department
of Natural Resources for their gracious cooperation in obtaining samples
vital to the conduct of this program.
61
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SECTION VII
REFERENCES
1. Epstein, M. M. and Widman, M. U., "Silt Stabilization Agents and
Application Equipment for Salvage Operation - Phase I", Contract
No. N62399-67-C-OOON (July 7, 1967).
2. Epstein, M. M. and Widman, M. U., "Polymer-Based Silt Stabilization
System and Application Equipment for Salvage Operations - Phase II",
Contract No. N62399-68-0028 (December 6, 1968).
3. "Algae Assay Procedure, Bottle Test", National Eutrophication
Research Program, p 82 (August, 1971).
4. "Standard Methods for the Examination of Water and Waste Water",
Thirteenth Edition, p 874 (1971).
5. CCC-T-191b, Federal Specification, Textile Test Methods (May, 1951).
6. Hester, F. E. and Dendy, J. S., "A Multiple-Plate Sampler for
Aquatic Macro-Invertebrates", Trans. American Fish Society 91,
pp 420-421 (1962).
63
-------
SECTION VIII
APPENDICES
Page No.
A. Results of Laboratory Investigation 66
Table A-l: Hot Melt Compositions 66
Table A-2: Coagulable Polymer Compositions Based on
Unplasticized Daran 220 Latex 68
Table A-3: Coagulable Polymer Compositions Based on
Plasticized Daran 220 Latex 69
Table A-4: Coagulable Polymer Compositions Based on
FR-S-257 Latex 70
Table A-5: Coagulable Polymer Compositions Based on
FR-S-194 Latex 71
Table A-6: Tabulation of Miscellaneous Latex
Experiments 72
B. Lists and Tabulations of Suppliers, Manufacturers and
Materials 74
Table B-l: Identification of Raw Materials 74
Table B-2: Tabulation of Commercially Available
Films 75
Table B-3: Code Identification - Film Manufacturers ... 76
C. Sample Calculations 78
Table C-l: Sample Calculations of Cost of Selected
Hot Melt Compounds 78
Table C-2: Sample Calculations of Cost of Alcohol
Soluble Nylon 79
65
-------
TABLE A-l. RESULTS OF QUALITATIVE TESTS OF HOT MELT COMPOUNDS
larpla H.. 501 3425 4-141 A-UJ LC 75 AL A-10 30 700 C Uulaloa. tc«p., ' Uurka
10-2
ll-l
17-1
11-3
no
10-)
12-4
no
ll-l
no
lt-2
lt-4
It-)
20-1
17-2
24-1
24-2
24-1
Samp It |to
10-1
11-2
U-4
11-5
S2-I
21-4
21-)
20-2
21-2
25-1
25-2
21-2
no
21-4
11-2
lt-3
21-1
Jfla-plt ftff
21-)
2t-l
2t-2
21-2
30-1
100 ..." " " • .... JJO
70 30*.- . . • ... . joo
10-70-- " • - ••• . jog
30 - - 70 - - - - ... . 2JQ
70 -*10. - • • --.. 2JO
J).... . . . 35 • • - 100
40.*-- - - . "|0.- 350
15 - - JO 75 • • • .... 250
34". SI 20 " • • ... . jj0
IS • - 50 2) - - « ... . jjg
70 • • 3) 20 • • • .... JOQ
70 - - 33 20 - - - ... • 230
7S---25 • • • .... JM
70 - • )) - 20 - • ... . joo
70--13- -~20 - ... . JQO
70--13- • • 10 ... . joo
70)0--- - - - -.. . ^oo
'0 • I) - - - It j50
50---- - - - .. . * 50 300
17.5 25 - - - ... J,.| ,00
37. J 3) • • • ... Jj.j ,50
IVA Vax Uai KL Utcotax Xlnaral (lyrval
too
70
70
15
22.5
SO
50
15
2S
25
10
43. J
It
2)
)J.»
tVA
17.)
35
J3.J
12. J
WP-
so
1)
2)
SO
t«
30
30 ..
S3 JO
S3.S 25
JO
JO ...
IS ...
SO . . 3J
50 - - 25
21 - - - 11
43.) ... H
50 ... . )4
JO ... . 35
50 ... . 11.)
IVA Vax
S2.5 10
31 10
17.5 30
17.5 SO
Ui> Vax Klyrval «lyr»al
IS
SO
IS
SO - IS
JO . .
SO ' • 11
100
3 SO
350
300
150
210
300
210
220
300
210
100
210
100
200
100
100
100
100
210
210
2 «0
110
100
171
Cood flaxlbllltyl (air taar ttronth
Ditto
Cood (laxibllltyt poor tfU •tr«n|th
Ditto
Pair flexibility) poor taar atrangtli
OHIO
Ditto
Ditto
loft, rubbary film; illghcl- ticky
Ditto
Ditto (blinded nn 1-roll Bill)
I*cill«nt (U>lblllt)ri poor t««r itronftb
Cood (Uxtbllltyl 9oor t«w •trtnirh
Ditto
Cood (Itxlbllltyl food t«*r «tr«n|':h
Wiak, ttrlatod (11
Cood rltxlbltltyl
Cood llolblllty)
'
"
Cood rlHlblllty;
cood n.«ibiiuri
Cood rioxlbllltyf
Cood (laElblllty;
Cood (Itilbllltyj
Cood llolbllltyl
Cood (loxlbllltyt
Oood UoKlbtlltyl
food t«tr itr«n|i:h
Ditto
Ditto
fair t*or ltran|r.h
POO |
poor toar itranfch
*
good t«ar atran|th
Ulc Caar atranf.h
(air taar atran|-.h
gnod taar atrang-h
poor taar atrang-h
(air toar atrang:b>
food tau Itranctll
-------
TABLE A-l. RESULTS OF QUALITATIVE TESTS OF HOT MELT COMPOUNDS
fiKOlo Ho.
10-2
ll-l
17-1
11-1
17-1
17-4
10-1
12-4
11-1
11-1
ll-l
ll-l.
11-1
ll-l
ll-l
ll-l
20-1
17-2
24-1
24-2
24-1
lonplo fO,
10-1
11-2
11-S
SI -I
21-4
21-40
21-1
20-2
21-2
25-1
21-2
21-2
21-1
ll-t
tl-t
U-l
15-J
21-1
2t-l
21-!
"•I
11-2
10-1
EVA
501
100
70
JO
10
70
JJ
to
IS
It
15
10
70
70
70
70
70
TO
SO
17.5
17.5
EVA
SOS
100
70
70
11
22.5
50
50
15
25
25
to
41.)
It
25
11.)
EVA
17.1
11
52.5
11.5
DPO-
1165
15
SO
11
10
1415
JO
10
Uox
10
10
10
IS
so
so
21
41. 1
SO
10
SO
EVA
52.5
IS
17.5
11.)
A-l',]
10
10
10
t~."?ililHi. mti ,r
A-1IJ A-ltS U 7S AL
JO
70
)0
JO )S
" 51 10 .
50 II
11 10 • *
11 10 . •
15
11 • 10
11 « - 10
Ji-
ll ..
2S
25 • •
Uu ret Plccotoi Mln.ril (lyrvol
10
11 10
12.1 -ll-
ll ..
11 • -
12
1J
Jt
IS
It. 5
WOR
JO
10
JO
so
A-l 65 60 75
so
II • •
11
11
A-SO JO 700 C Eoullloo Trap., 1
... • jjo
• • 250
ISO
11 .-• JOO
• (0 jjo
250
. ... • joo
110
• JOO
JOO
JOO
10 .... jo,,
.... 100
* . * 11 • 350
• ... so joo
• ... ly.J 300
17.5 }JO
100
ISO
300
ISO
210
200
260
220
JOO
210
JOO
a 10
200
100
JOO
JOO
JOO
JOO
210
no
110
JOO
1)1
Cood
Good
Cood
tneo
nlr
lo (e
Cood
Cood
Cood
Cood
.Good
Book
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
Cood
COM
(lo.lblll,,,
PMClbU
flixibiuty;
, rubbery fit
fli.ilb.Hiy;
fUvtbllltyi
ll.nl flKlbl
flexibility,
a.xibUity;
flexibility!
Ditto
OUt»
poor ttur
RfjBuirkt
(tr*n|th
Ditto
poor teer etrer>|i.h
ffjlr tiu ttr*fi|'.h
Pit II
Dltt«
titto
•1 •Hghtt" t«chy
It ct" »tt«n|Ch
Ditto
Ditto
Ditto «(•
-------
TABLE A-2. COAGULABLE POLYMER COMPOSITIONS BASED ON
UNPLASTICIZED DARAN 220 LATEX
oo
Experiment
Number
33-1
33-2
33-3
34-1
34-2
5-1
5-2
5-3
5-4
6-2
6-3
6-4
7-1
18A-1
28-1
18B-1
28-2
18B-2
28-5
18F-1
28-3
18F-2
28-6
28-4
28-7
Coll&d(a)
...
...
...
Gelva C3V3Q
PA-6
PA -10
Kelgin LV
PA-6
PA- 10
Kelgin LV
Kelgin LV
Kelcosol
Kelcosol
Superloid
Superloid
Superloid
Superloid
Keltex
Keltex
Keltex
Keltex
Kelgin HV
Kelgin HV
Colloid
on Latex
Solids, 7.
—
—
...
...
...
25
25
25
3.3
25
25
3.3
3.3
1.6
3.3
1.6
3.3
0.85
1.6
1.6
3.3
0.85
1.6
3.3
1.6
Total
Polymer
Solids, 7.
61
61
61
61
61
38
38
38
31.5
38
38
31.5
31.5
31
31.5
31
31.5
41
41
31
31.5
41
41
31.5
41
Coagulation
Bath
NaOH
HCl
HCl
A12(S04)3
FeCl3
...
HCl
HCl
HCl
HCl
HCl
HCl
FeCl3
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
Coagulation
Bath Con-
centration, 7.
20
5
20
20
20
5
5
5
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Remarks
Very weak film
Very weak film; easily redispersed
Strong, brittle film; very rough
surface
Very brittle, crumbly film; sepa-
rated into layers
Hard, brittle, crumbly film; some
separation into layers noted
Incompatible solution
Poor film, easily redispersed
Ditto
M
ii
ii
Fairly weak film
Ditto
ii
ii
Somewhat stronger film; brittle
Ditto
ii
ii
Fairly weak film
Ditto
ii
it
ii
it
(a) For fuller identification see list of raw materials in Table B-l.
-------
TABLE A-3. COAGULABLE POLYMER COMPOSITION BASED ON
PLASTICIZED DARAN 220 LATEX
Experiment
Number
31-1
31-2
31-3
31-4
36-1
36-3
36-2
36-4
52-1
57-1
5ii-l
511-2
74-1
Colloid ^
Superloid
Suparloid
Suparloid
Sup«rloid
...
— — —
Superloid
Sup«rloid
Superloid
Superloid
Superloid
Colloid Plasticizer
on Latex , , on Latex
Solids, 7. Plasticizer ' Solids, 7.
0.85
0.85
0.85
0.85
...
" " "
0.65
0.65
0.33
0.33
0.65
Santicizer E-15
Santicizer 141
Santicizer B-16
Flexol TOF
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
Santicizer E-15
8.2
8.2
8.2
8.2
32.8
19.7
16.4
12.3
16.4
20.5
20.5
20.5
14.8
Total Coagulation
Polymer Coagulation Bath Con-
Solids, 7. Bath centration, 7, Remarks
39 HC1
39
39
39
50.8
54.5
55.5 HC1
56.7 HC1
47.2 A12(S04)3
46.3 HC1
51.4 HC1
51.4 A12(S04)3
47.6 HC1
10
...
...
20
20
10
20
20
20
20
Fair emulsion stability;
improved film flexibil-
ity
Unstable mixture
Ditto
ii
ii
n
Strong, flexible film
Strong film; slightly less
flexible and more surface
roughness than 36-2
Strong film; still some-
what brittle
Strong, flexible film;
high modulus of elas-
ticity on aging
Strong, flexible film;
some surface roughness
Strong, hard film; poor
flexibility
Strong, flexible film
(») For fuller identification see list of raw materials in Table B-l.
-------
TABLE A-4. COAGULABLE POLYMER COMPOSITIONS BASED ON FR-S 257 LATEX
Colloid
Experiment , v on Latex , v
Number Colloid V ; Solids, 7, Filler*1 '
16-3
34-3
34-4
29-1
29-2
29-3
35-1
35-2
42-3
42-4
42-5
42-6
26-1
39-2
39-1
40-2
46-1
46-2
47-1
47-2
...
...
Superloid
Superloid
Superloid
Superloid
Superloid
Kelgin LV
Kelgin LV
Kelgin LV
Kelgin LV
Gelva C_V-_
CMC R-75H
CMC R-7511
CMC R-75XL
...
Superloid
Superloid
...
...
0.4
0.8
0.8 Ti02
0.4
0.8
1.0
1.0
12
12
30
0.3
3
20
— Sulfur
Sulfur
0.8 Zinc
0.8 Zinc
Filler Total Coagulation
on Latex Polymer Coagulation Bath Con-
Solids, 7. Solids, 7. Bath centration, 7. Remarks
50
50
50
42
42.4
10 42.4
42
42.4
45.8
45.8
25.
25
32.5
47
25
30
40 41.7
40 41.7
40 35
40 35
HCl
FeC13
A12(S04)3
HCl
HCl
HCl
HCl
HCl
HCl
A12(S04)3
HCl
A12(S04)3
HCl
A12(S04)3
A12(S04)3
A12S04)3
HCl
A12(S04)3
HCl
A12(S04)3
20
20
20
20
20
20
10
10
20
20
20
20
20
20
20
20
20
20
5
20
Strong, flexible film; rough
surface
Brittle film; rough surface
Brittle film; rough surface
Strong, flexible film, rough
surface
Strong, flexible film
Strong, flexible film
Fairly strong, flexible film;
rough surface
Fairly strong, flexible film
Strong, flexible film
Weak, brittle film
Weak, brittle film
Fairly strong, hard film
Fairly strong film; unstable
solution
Fairly weak, flexible film;
some surface roughness
Fairly weak, flexible film
Weak, crumbly film
Weak, crumbly film
Fairly strong, flexible film;
rough surface
Very weak film^b)
Weak, crumbly film
(a) For fuller identification see list of raw materials in Table B-l.
(b) In spite of the reduced HCl concentration and shortened contact time, the film developed numerous gas bubbles soon
after immersion.
-------
TABLE A-5. COAGULABLE POLYMER COMPOSITIONS BASED ON FR-S 194 LATEX
Experiment
Number
16-2
18C-1
18C-2
18C-3
18C-4
18D-1
18D-2
18D-3
18D-4
18G-1
18G-2
18G-3
18G-4
26-3
26-4
Colloid (a)
Kelcosol
Kelcosol
Kelcosol
Kelcosol
Superloid
Superloid
Superloid
Superloid
Keltex
Keltex
Keltex
Keltex
Gelva C3V3Q
Gelva C V
Colloid
on Latex
Solids, 7.
1.6
0.8
0.3
0.15
1.6
0.8
0.3
0.15
1.6
0.8
0.3
0.15
12
50
Total
Polymer
Solids, 7.
63.3
32.2
42.5
52.9
58.1
32.2
42.5
52.9
58.1
32.2
42.5
52.9
58.1
47.2
31.1
Coagulation
Bath
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
HC1
Coagulation
Bath Con-
centration, 7.
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Remarks
Very much shrinking
Fairly strong, flexible film
Slightly stronger than 18C-1
Slightly stronger than 18C-2
Slightly stronger than 18C-3;
rough surface
Fairly strong, flexible film
Ditto
Fairly strong, flexible film;
slight surface roughness
Fairly strong, flexible film;
rough surface
Fairly strong, flexible film
Fairly strong, flexible film;
slight surface roughness
Slightly stronger than 18G-2;
rough surface
Slightly stronger than 18G-3;
rough surface
Fairly strong, flexible film
Strong, hard film; much shrinkage
(a) For fuller identification see list of raw materials in Table B-l.,
-------
TABLE A-6. TABULATION OF MISCELLANEOUS LATEX EXPERIMENTS
Experiment
Number
16-4
26-2
16-5
53-2
55-1
55-2
62-1
62-2
53-3
54-1
vj
o 54-2
53-1
56-1
56-2
61-1
61-2
66-1
Latex(a)
FR-S
FR-S
FR-S
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
FPC
2003
2003
2004
790
790
790
790
790
7299B
7299B
7299B
XR7351
XR7351
XR7351
XR7351
XR7351
XR7351
Colloid (a)
Gelva C3V3Q
Superloid
Superloid
...
Superloid
...
Superloid
Superloid
Superloid
Superloid
...
Superloid
Superloid
Colloid Plasticizer
on Latex . . on Latex
Solids, 7. Plasticizerv ; Solids, 7.
25
--
0.
0.
--
0.
..
0.
0.
-•
0.
0.
--
0.
0,
Total
Polymer
Solids, 7.
... 59.2
37.1
60.0
.
8
8
Santicizer E-15 30
8 Santicizer E-15 30
* •*• ••*
8
8
,.
8
8
Santicizer E-15 30
,8 Santicizer E-15 30
,8 Santicizer E-15 20
50
42
42
43
29
56
47
47
50
42
42
43
29
.0
.0
.0
.5
.7
.0
.0
.0
.0
.0
.0
.5
.7
Coagulation
Bath Con-
centration, %
HCl
HCl
HCl
HCl
HCl
A123
HCl
HCl
HCl
HCl
A12(SOA)3
HCl
HCl
A12(S04)3
HCl
HCl
38.8 ^SO^
*. T
Coagulation
Bath Remarks
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
50
Very much shrinkage
Fairly weak film; poor elasticity;
about 25 % shrinkage
Very much shrinkage
Very rough surface
Very weak film
Weak, crumbly film
Very soft, weak film
Soft, fairly weak film
Very rough surface
Fairly strong, hard, flexible
film
Fairly strong, hard film;
poor flexibility
Very rough surface
Fairly strong film;
poor flexibility
Weak, brittle film
Poor film formation
Weak film; poor flexibility
Fairly strong, flexible film;
somewhat rough surface
(a) For fuller Identification see list of raw materials in Table B-l.
(b) Calculated on preplasticized latex solids.
-------
TABLE A-7. ELVAMIDE 8061 COMPOSITIONS
Experiment Elvamide
Number Concentration,
69-1
69-2
69-3
69-4
71-1
72-1
72-2
72-3
73-1
10
10
25
23.8
10
25
20.8
22.6
25
Water, % of Filler on
% Alcohol total solvent Filler Elvamide, 70
Ethanol
Methanol
Methanol
Methanol
Methanol
Ethanol
Ethanol
Ethanol
Ethanol
10
20
20
20
20
20
20
20
10
..-
Ti02
Avibest-C(b)
Ti02
Ti02
...
\—
20
10
80
40
—
(a) Du Font's Elvamide 8061, alcohol-soluble nylon.
(b) For further identification see list of raw materials in Table B-l.
73
-------
tAlU l-l. IDEXTiriCATIOM Or RAW HATCH UU
Tcada N.~
Latlcas
Daraa 220
M-S J57
n-s 19*
n-s 2003
n-s jo«
rrc 790
rPC 72991
TK IR7351
telcuol
teljla EV
bllln LV
lalMx
Sup«rlolt!
CMC I-75-B
OC I-75-IL
«•»« ST30
»A-«
rx-io
7l«stlctzeri
Santlclrcr 1-15
Santlcitcr 1-16
fentlcliar 141
riaxoi TOT
folvrnt STStea Corrpcnent*
Ilvaaida 8001
110,
Avlbost-C
yolyggrt
»VA 501, 505 & 508
PFD-6169 & 9169
MA-9300 & 9500
ftt-700
AC-5M
Kxilflars
Uyrvtl 30, 60 t 75
riceotsz 1C 4 75
IlccoUstlc At fc 1-50
Tnffln 30
Kloaral oil
fpolanc C
Alphalt aautsloa
ralvvxi 2COO
ArUtovai A-R3 t A-K5
fun 3425 4 4417
AcroM.C
^ZTuat
Urrtt*
(utfur flo**™
0«icripcton
Cae*l/t>tl.tic AtJiydrld* copolyoer
fhchatlyl clycol«t* titer
Ditto
fhoeptite «iter
Trl (2-«thylhcxyl) pbo*Ph*C«
I.I7..U. t.r,oly«r
Anat... tltaal.. dl=xt4., trad. FT'
Klcroerrstalllaa slllcata
lot Halt Hands
fthylana vinyl acauta
Cthylana athyl acrylata
Ithylau acrylic acid
*foljcaprolactoo*
Cthylaoa or(aale acid
Lov aolacular v«l(ht volyvtnyl.c.
Tloyl toluaoa copolycxr
Ditto
IVA/vax bland
Kioto 1 oil
T olywtttylan.. vax
Aaphalt
Lov aolacular v«l({it p«ly*thyl«i>.
Paraffin vax
Ditto
Klcroaryatallin* «ax
IlM
larlu* fulfils
iulfur
Hfnufacturar
Craca Organic Ch«»tcslf
Tlrvstooa Synthatle Rubbar and
La tax Conp«ny
Dtlta
«
•
Flrcsteo. flsstlcs Covpsny
Dltu
"
Kalett Cossanv
Ditto
«
•
«
I.I. Da font 4s Keaaun sod Co.
Ditto
• IfeojaQto Coopanj
Colt Oil Optical Company
Ditto
KooMUo Coepany
Ditto
•
Dnl«a Carblda Corporation
l.t. &n font da ".ctoours and Co.
Ditto
fIC Corporation
Cnloa Carblda Corporation
Ditto
•
•
Alll*4 Cbevlcal Covpaoj
taUlcol Cb«aUal Corpora t too
Y.ttnjtjlvsala Ic4u
-------
TABLE B-2. TABULATION OF COMMERCIALLY AVAILABLE FILMS
(a)
Listed in Decreasing Order of Density
Film Type
Vinylidene-vinyl chloride
Cellophane
Polyester (Mylar)
Vinyl Chloride-Acetate, non-
plasticized
PVC, solvent cast, non-plasticized
Cellulose Acetate
Cellulose Triacetate
PMMA, Korad A, white
Polysulfone
Polyvinyl Alcohol
PVC, plasticized
PVC, non-plasticized
Vinyl Chloride-acetate, plastieized
PVC, solvent cast, plasticized
Cellulose Propionate
Polycarbonate
Cellulose Acetate Butyrate
PMMA, oriented
PMMA, Korad C
Ethyl Cellulose
Nylon 6/6
Nylon 6
Polyurethane
Rubber Hydrochloride
Vinyl-nitrile rubber alloy
Polystyrene, oriented
ABS
Nylon 11
Nylon 12
Polyethylene - HD
lonomer
Polyethylene - MD
Ethylene/Vinyl acetate
Polyethylene - LD
Polypropylene - biaxially oriented
Polypropylene - cast
Specific
Gravity
1.59-1.71
1.40-1.50
1.38-1.41
1.30-1.40
1.30-1.40
1.28-1.31
1.28-1.31
1.26
1.24-1.35
1.21-1.31
1.20-1.80
1.20-1.50
1.20-1.35
1.20-1.35
1.20
1.20
1.19-1.20
1.18-1.19
1.17
1.15
1.14
1.13
1.11-1.24
1.11
1.10-1.30
1.05-1.06
1.04
1.03
1.01
.941-. 965
0.940
.926-. 940
.924-. 950
.910-. 925
.902-. 907
.885-. 895
Thickness
Range,
mils
0.4-0.6
0.75-1.7
0.15-14
0.8-40
1-4
0.5-350
0.8-20
1.5-6
2-225
0.5-12
0.5-80
0.6-75
0.8-10
1-10
3-30
0.25-500
1.1-350
5-10
2-6
2-15
5-20
5-30
0.5 & up
0.4-2.5
1-3
0.25-20
10-500
1-50
0.5-60
0.4 & up
1-10
0.3 & up
0.75 & up
0.3 & up
0.5-1.5
0.87 & up
Maximum
Width,
inches
68
67
120.
72
54
60
46 /VN
62 (b)
52
54
96
84
84
54
48
54
48
43,
62 (b)
42
20
84
68
60
54
76
105
28
--
60
60
240
480
480
72
60
(a) Modern Plastics Encyclopedia, Vol. 48, No. 10A, 1971-1972. This
information is not all-inclusive; for instance, Nylon 6 is known to
be available in 2-mil thickness.
(b) To 108 on custom basis.
75
-------
• TABLE B-3. TABULATION OF FILM MANUFACTURERS
Generic Film Type
Regenerated cellulose
Cellulose acetate
Cellulose triacetate
Cellulose acetate butyrate
Cellulose acetate propionate
Ethyl cellulose
Polyacrylonitrile
Polyamide
Polycarbonate
Polyester
Polyethylene
Polypropylene
Polystyrene
Polyvinyl alcohol
PVC, flexible
PVC, rigid
PVDC
Rubber hydro chloride
Trade Name
Cellophane
Cellophane
Kodacel
Kodacel
Kodacel
Forticel
Ethocel sheeting
Barex
Capran
Fosta
Lexan
Celnar
Mylar
Kodar
Polyfilm
Visqueen
Zendel
Udel
Pro-fax
Kordite
Trycite
Polyflex
Eeynolon
Resinite
Velon
Vita film
Reynolon
Oriex
Vynex
•Mirrex
Saran Wrap
Cryovac
Plioflini
Manufacurer
(5)
(16)
(6)
(6)
(6)
(3)
CO
(18)
(1)
(9)
(10)
(3)
(5)
(6)
CO
(7)
(20)
(20)
(13)
(1*0
CO
(15)
(17)
(2)
(8)
(11)
(17)
(19)
(19)
(19)
CO
(12)
(11)
(a) Plastics Fila Technology, W. R. R. Park, editor, Van Kostrand Heinhold
Co., New York, 1969, pp. lW-1^5
fb) For code identification of manufacturers see Table B-4.
76
-------
TABLE B-4. CODE IDENTIFICATION - FILM MANUFACTURERS
Code Manufacturer
(1) Allied Chemical Corp., Plastics Division, Morristown, N.J.
(2) Borden Chemical Div., Borden, Inc. New York, N.Y.
(3) Celanese Plastics Company, Newark, N.J.
(4) Dow Chemical Co., Midland, Michigan
(5) E. I. Du Pont & Co., Wilmington, Delaware
(6) Eastman Chemical Products, Kingsport, Tenn.
(7) Ethyl Corp, Industrial Chemicals Div., Baton Rouge, La.
(8) Firestone Plastics Co., Potts town, Pa.
(9) Foster Grant Co., Leominster, Mass.
(10) General Electric Co., Plastics Dept., Pitts field, Mass.
(11) Goodyear Tire & Rubber Co., Plastic Film & Sheeting Dept.,
Akron, 0.
(12) W. R. Grace & Co., Polymers & Chemicals Div., Cambridge, Mass.
(13) Hercules Incorporated, Wilmington, Del.
(14) Mobil'Chemical Co., Films Dept., Masedon, N.Y.
(15) Monsanto Company, St. Louis, Mo.
(16) Olin Corp., Plastics Operations, Stamford, Conn.
(17) Reynolds Metals Co., Richmond, Va.
(18) Vistron Corp., sub. SOHIO, Cleveland, 0.
(19) Tenneco Chemicals, Inc., Tenneco Plastics Div., Piscataway, N.J.
(20) Union Carbide Corp., Chemicals & Plastics, New York, N.Y.
77
-------
APPENDIX C-l
SAMPLE CALCULATIONS OF COST OF SELECTED
HOT MELT COMPOUNDS
Material Price
Price; $/lb
EAA-9500 0.535
EAA-9300 .70
EVA-501 .59
EVA-505 .54
DPD-6169 .315
DPD-9169 .315
Klyrvel-30 .24
Klyrvel-60 .24
Aristowax .16
Barytes .02
Wt.
grams i Wt., 7. Price, $ Total Cost, $
EVA 50i 25
Klyrvel 30 25
Aristowax A-143 50
Barytes 20
120 100.0 $0.236
DPD-6169 (EEA) 20.8 x .315 - .065
Klyrvel 30 20.8 x .24 = .050
Aristowax A-143 41.7 x .16 = .067
Barytes 16.7 x .02 = .003
$0.185
78
-------
APPENDIX C-2
SAMPLE CALCULATIONS OF COST OF ALCOHOL-SOLUBLE NYLON
Ib.
lof) 150
37.5
62.5
62.5
312.5
gal.
22.78
4.50
6.80
1.69
35.77
J_
12.30
112.50
1.25
126.05
Materials
EtOH (190 proof)
Water
Elvamide 8061
Barytes
d = 1.047 = 8.736 Ib/gal
Cost = $0.405/lb = $3.53/gal
= $0.0093/ft2/dry mil
79
-------
SELECTED WATER i. Rcr--tNo.
RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
W
POLYMER FILM OVERLAY SYSTEM FOR MERCURY CONTAMINATED
SLUDGE - PHASE I
5, R- ortD: :
6,
S, Pf-foTinir' Ofgar'-ation
Epstein, M. M.
Widman, M. U.
BATTELLE
Columbus Laboratories
Columbus, Ohio 43201
16080 HTZ
68-01-0088
13, Type -: " Repo: -»n
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