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Freezetch
Freezetch
Freezetch
by
MARY BETH KEFFER BRAY, B.S. in C.E.
A THESIS
IN
CIVIL ENGINEERING
Approved
Accepted
December 1989
THE USE OF PASSIVE COOLING TECHNIQUES TO
by
MARY BETH KEFFER BRAY, B.S. in C.E.
A THESIS
IN
CIVIL ENGINEERING
Approved
Accepted
December 1989
T3
Mo. i^1
ACKNOWLEDGEMENTS
and understanding. His professional expertise together with his valuable assistance,
Appreciation is extended to Dr. Richard Tock and Dr. Tony MoUhagen for the time
Tech University, for his support in the experimental phases of this project.
cations Center in the Engineering College at Texas Tech University, for her help with
proof-reading.
Special thanks are also extended to Dean Bray, Veen Chee Foong, June Wilcott
Sligar, and all the other people who offered assistance and support throughout this
The financial support received from the U. S. Air Force is also greatly appreciated.
11
TABLE OF CONTENTS
ACKNOWLEDGEMENTS ii
LIST OF TABLES v
LIST OF FIGURES vi
NOTATIONS vii
CHAPTER
1. INTRODUCTION 1
The Need for Energy Conservation 1
Background 1
Objectives 3
Thesis Outline 4
2. LITERATURE REVIEW 5
m
3. PROCEDURES 22
Approach 22
Research Plan and Procedures 23
Outdoor Tests 23
Controlled Conditions Tests 24
Test Facility 25
Outdoor Test Facility 25
Controlled Test Facility 26
Ion Chromatograph 26
Data Analysis 27
Outdoor Test Phase 27
Controlled Test Phase 29
Revised Controlled Test Phase 29
Stephan's Equation Analysis 30
4. RESULTS 31
Data Presentation 31
Outdoor Test Phase 31
Controlled Test Phase 32
Revised Controlled Test Phase 33
Stephan's Equation Analysis 35
Economic Analysis 36
5. CONCLUSION 39
Recommendations 39
BIBLIOGRAPHY 41
APPENDIX 45
IV
LIST OF TABLES
1 OSW Projects 46
2 Freeze-evaporation Process 47
3 Direct-refrigerant Freeze Process 48
4 Water Phase Diagram 49
5 Iranian Ice-maker 50
6 Ice Crystal 51
7 Natural Arctic Ice 52
8 VFMPT Process 53
9 VFMPT Phase Diagram 54
10 IFC Process 55
11 Test Unit 57
12 Results from 500 mg/1 Test Run 62
13 Results from 1500 mg/1 Test Run 63
14 Results from 4500 mg/1 Test Run 64
15 Average Results 65
16 Average Results with Seawater 66
17 Proposed Passive Ice-maker Ponds 67
VI
NOTATIONS
h = Thickness of Ice
IC = Ion Chromatograph
Qc = Convective Flux
Qk = Conductive Flux
Vll
RO = Reverse Osmosis
t = Time
p — Density of Ice
0 — Temperature
Vlll
CHAPTER 1
INTRODUCTION
The world's sources of gas and oil, the most desirable form of fossil-fuel energy, are
being depleted. The United States is using oil faster than any other nation in the world
but has less than 5 percent of the world's oil reserves. The amount of oil produced in
the United States is already decHning. Pakiz (23) predicts that the United States will
run out of oil between the years 2050 and 2100. Therefore, it is necessary to utilize
other energy sources or to find methods that are less energy intensive for accomplishing
Background
Utilization of passive cooling is one way that fossil-fuel energy consumption could
be decreased. Passive cooling uses the natural environment to reduce the temperature
of a substance instead of using energy intensive devices. This technique has been used
in Iran for air conditioning, refrigeration, and to make ice (3). The ice-maker process
consists of a system of shallow ponds which are 10 to 20 meters wide and 100 meters
long or longer. An adobe wall runs along the south side of the pond and provides
shade during the day. The wall also acts as a wind block and prevents heat gain from
convection. Water is added on winter nights. This water is cooled by the transfer of heat
from the water to the atmosphere by radiation, evaporation, and conduction. However,
the water body gains heat through conduction from the underlying soil. This heat must
be removed by heat transfer to the atmosphere. The ponds lose a large amount of heat
through radiation to the sky on clear nights. Heat is also lost when water molecules on
the surface evaporate. When the night is cool enough, ice will form (3).
CooHng a material involves the loss of heat through evaporation, radiation, or con-
vection (25). This heat loss is affected by the specific heat of a substance, the heat
required per unit mass of the substance to raise its temperature by 1 degree Celsius
(27). The specific heat of water is 1 calorie per gram per degree Celsius and is the
Radiation is heat transfer without mass transport. At night, the air wiU be cooler
than the water and heat will be transferred by radiation to the sky or black space.
Convection is heat transfer by fluid motion. Cool air passing over the water will
gain heat from the water whereas hot air passing over the water wiU heat the water (3).
Evaporation is the change of state from liquid form to vapor. Heat is lost because
the water must overcome the latent heat of vaporization which is the amount of heat
dissolved solids in water. When water freezes, it tends to freeze as a crystal and dissolved
solids will be excluded from the crystal matrix as the ice crystals develop. The ice formed
wiU be more pure than the liquid portion, because the latter includes the substances
excluded from the frozen crystal. This technique could be used to desalinate or remove
If this technique could be optimized, it could be used during part of the year in
most areas of the United States. The operational scheme behind passive cooling is to
minimize the heat input into the substance during the day and maximizing the heat
loss at night, allowing the water to freeze. By optimizing the ways to limit heat input,
passive cooling ice-makers may be an alternative and more economical way to freeze
water. The resultant ice would be a natural product from environmental processes and
not from energy intensive-methods. However, there axe costs associated with passive
cooling. The operating costs for the system consist of energy costs to run the ice-removal
equipment and pump the water; and maintenance costs, and labor costs. The capital
costs for the system consist of site acquisition fees, and construction costs for the ponds,
walls, appurtenances, and equipment costs for the ice removal and washing equipment.
Objectives
This study wiU look at the use of freezing to remove total dissolved solids (TDS)
from waste waters. The purpose is to find out if the freezing of water under winter
conditions could be used as a more economical means of removing dissolved solids. The
1. To determine what quality water can be obtained from ice formed from
Thesis Outline
The next chapter includes a review of pertinent literature in the area of passive cool-
ing, the dynamics of cooling, the climate of the ground layer, freezing technology, and
the properties of water. Chapter 3 describes the acquisition of data used in this study
and the procedures that were adopted to perform the laboratory tests. A discussion of
the results is presented in Chapter 4. Finally, the conclusions of this research as weU as
LITERATURE REVIEW
This chapter is divided into four sections. The first section discusses the need for
economical methods to treat waters with high TDS content. The second section dis-
cusses passive cooling. The third section discusses dynamics of coofing, the climate
near the ground, and how the climate effects the cooUng of small bodies of water. The
fourth section discusses the properties of ice that allow freezing to be used as a method
of solids concentration. The fourth section also discusses two industrial processes that
Fresh water costs less per gallon or ton in the United States than any other commod-
ity on the market (31), but predictors from the 1950's believed that fresh water supplies
would run out in the 1980's. The demand for water in this country was predicted to
exceed the dependable fresh water supply in 1980 (28). To help alleviate this problem,
the Saline Water Act was passed by Congress in July 1952. The act authorized the cre-
ation of the Office of Saline Water (OSW) and funded OSW with a budget of 2 million
dollars for a 5-year period for investment in research and development of saline water
resources (8). In 1955, the law was amended to extend the program over 10-year period
with a 10 million doUax budget (8). In 1958, another 10 miUion dollars was authorized
to build pilot plants (31). The program funded the building of six different plants which
for less than a dollar per thousand gallons. Figure 1 in the Appendix shows the plant
locations.
and direct refrigerant cooling will be examined in more detail. Two different techniques
were considered for the freeze separation processes. Plants utilizing each technique were
eventually built. The first pilot plant built utilized a freeze-evaporation process and the
enough for ice crystals to form (26). The water vapor generated in the process can
also be used as a source of desalinated water. The pilot plant consists of four 60,000
gallons per day modules. No cost analysis was available for the operation (26). In the
form. Use of the direct refrigeration process reduces the size of the compressor but adds
the problem of handling a second fluid which must be removed from the system (8).
This 15,000 gallon per day pilot plant produces water in the range of 35 to 45 cents per
thousand gallons (8). Schematics of both plants are shown in Figures 2 and 3.
Usable Water
The primary application that wiU be addressed in this study is the desalination
of water containing high levels of inorganic dissolved soHds. For water to be used in
many applications, certain constituents must not exceed specified limits. These limits
are dependent upon the intended use of the water. Water that contains less than
500 milligrams per liter of total dissolved solids is classified as fresh by the United
States Public Health Service (31). Also, the Environmental Protection Agency (EPA)
recommends that drinking water not exceed 500 miUigrams per liter total dissolved
solids (TDS) according to the 1980 standards. At 500 milligrams per liter, the water
wiU begin to have a salty taste. Cities such as Lubbock, Texas, exceed this limit with
liter is recommended but no maximum contaminant level has been set for TDS (22).
Water used for irrigation can have 500 milligrams per liter TDS. Waters can be used at
higher salinity levels except when the local water table is close to the ground surface.
Waters with TDS concentrations of 5,000 milligrams per Hter and greater are generally
not acceptable for any irrigation uses (37). Thresholds for cooling water salinity levels
Dynamics of Coohng
Cooling is achieved through the loss or transfer of heat. When water is cooled, it
loses heat by radiation, evaporation, and conduction (38). These methods transfer the
water's heat to the air. More specifically, radiation is the emission, dissemination, or
diffusion of heat from the water to the surrounding materials. Radiation is a function of
water surface area and water temperature. Evaporation is the change of state from liquid
to vapor. Heat is lost because the water must overcome the latent heat of vaporization,
the amount of heat required to change a molecule of liquid to a gas. A fluid in the
form of a gas must have more energy than its liquid form. Liquid at the point where it
is about to evaporate and gas from the liquid that has just evaporated may be at the
same temperature. The only difference between the two is their energy levels. The extra
energy in the gas is contributed by the surrounding Hquid molecules before it vaporizes.
8
The heat lost through this process is difficult to determine since it is dependent on
ambient meterological conditions (38). The phase diagram in Figure 4 shows the states
would occur by the transfer of heat from the basin soil underlying the water to the water
and then from the water to the atmosphere. Convection is the transfer or conveyance of
heat by moving fluids. Fluid motion transfers heat between regions of unequal density
both in the body of water and between the water body and the overlying atmosphere.
Wind passing over the water can transfer some of its energy to the water as heat or pick
up heat from the water depending on the existing temperature gradient. The wind can
increase the heat content of the water and thus wind effects in passive-cooling ice-maker
systems must be minimized. Convection and conduction-like radiation axe also difficult
to estimate because they, too, are functions of local meterological conditions (38).
The optimal cooling scenario is a fiat pond that is exposed to the entire hemisphere
of the night sky. When the sky is clear and the humidity is low, 20 to 30 BTU per
The interaction of the different methods of heat transfer are described by Pounder
Qk = Qr + Qc + Qc (2.1)
where Qk is the conductive flux, Qr is the radiative flux, Qc is the convective flux, and
e
k - d t = L/9dh (2.2)
h
thickness of the ice, L is the latent heat, and p is the density of the ice.
that has already formed on a large body of water. The calculated thickness is the ice
that will grow or decay from the bottom layer of the ice sheet due to heat transferred
by conduction. Since this equation only considers conductive heat transfer, it is limited
in its uses.
examine the optimization of cooling by solar ponds. Tests were run to determine the
amount of cooling due to each process and the total maximum cooling that could be
achieved through natural processes at night. Four water-proofed, insulated boxes were
used to hold the water. The first box, with the top covered with foil to prevent heat loss
by radiation, measured the heat lost by convection. The second box was covered with
a black plastic film to maximize radiation losses. The third box was uncovered to aUow
evaporative losses while the fourth box utilized spray evaporation to maximize cooling
(16).
The study found that convection losses from the water gradually decreased water
temperatures and this loss lagged behind the dry-bulb temperature. When convection
10
and radiation were utifized, the water temperature followed the dry-bulb temperature.
The water temperature in the third box fell below the dry-bulb temperature shortly
after sunset and sometimes fell below the wet-bulb temperature. In the fourth box, the
temperature fell below both the wet-bulb and dry-bulb temperatures and sometimes
the water temperature dropped below the dewpoint before sunrise. The temperature in
the spray-evaporation process was the most effective. This process increased the cooling
Passive Coohng
Passive cooling is the use of the natural environment to decrease the temperature
of a substance through the natural fiows of thermal energy under ambient conditions
(24). The second law of thermodynamics says that heat fiows from hot to cold regions
or from high pressure to low pressure zones. Passive cooHng techniques utilize this law
by allowing the excess heat in a system to flow to a sink exhibiting a lower temperature
2. has few moving parts which are durable, and, therefore, requires
4. Is safe.
Passive cooling systems have evolved over the years to improve man's comfort. In
arid, interior, continental areas where the ambient air temperature exhibits a large
variance from day to night, buildings are built with thick walls, domed roofs, and
with common walls or Uttle distance between adjacent structures. The thick walls offer
insulation and also act as heat reservoirs which dampen the daily temperature variations
inside the home. The domed roofs and the clustered buildings help decrease the solar
energy input into the home. The side-by-side construction of buildings also help shade
the streets and adjacent buildings. These adaptations are examples of age-old techniques
(3). The principles used in these adaptations can also be applied today in other regions.
Other iimovations that have been used for years in the Middle East include the wind
tower, the cistern, and the ice maker. The wind tower sensibly and evaporatively cools
air. The air is directed over an underground storage pond and then is circulated through
the area to be cooled. Cisterns holding runoff from building roofs or water brought from
local supplies, can be the source of the coohng water, or can act as a heat-sink from
the air within the buildings. The ice-maker technique consists of a system of ponds
and an ice-storage building. When ice forms in the ponds, it is removed and stored.
To lower interior building temperature, the ice storage facility is constructed partially
underground to help preserve the ice. The ice-maker has been used to produce ice when
The ice-maker concept could have appHcations in other parts of the world. The
ice-maker system as used in Iran consists of several shallow ponds, 10 to 20 meters wide
and several hundred meters long (Figure 5). An adobe wall runs along the south side
of the pond and provides shade during the day. The wall also acts as a wind block at
night, preventing heat gain from convection. Several ponds and walls can be placed in
12
parallel. This placement increases the shielding effect from the wind. Water is added to
the ponds on winter nights. The pond water is then cooled by the transfer of heat from
the water to the atmosphere through the combination of radiation, evaporation, and
conduction processes. However, the water body gains heat through conduction from the
underlying soil which must be dissipated to the air. The water will lose a large amount
of heat through these processes on clear nights. When the night is cool enough and
these processes are active, ice wiU form (3). The ambient air temperature determines
how much ice will form. On some nights, water is added in centimeter increments at
periodic intervals during the night to increase the amount of ice formed. In areas similar
in cUmate to Iran, passive cooling systems may be feasible and economical (3). These
To understand why passive cooling works, the chmate near the ground must be
examined. Water has a high specific heat and thus acts as a heat reservoir. Specific
heat is the heat required per unit mass to raise the temperature of the substance by
1 degree Celsius (27). The specific heat of water is 1 calorie per gram degree Celsius
and is the standard to which other materials are compared. For a dry mineral soil, this
value is about 0.2 calories per gram per degree Celsius even if the specific composition
The soils that surround the ponds are important in the formation of ice. Different
soil types wiU transfer heat at different rates. The optimal soil would be a poor insulator,
like sand. The average specific heat capacity of soil can be taken as the average of its
constituents. In other words, a body of water will change in temperature much less
13
than the adjacent land areas or the air bodies for the same weather conditions. The
specific heat of ice is independent of its density and the specific heat of any air bubbles
trapped in the ice may be neglected. The specific high heat of water makes passive
cooling possible.
Small bodies of water wiQ show greater sensitivity to temperature changes than
larger ones. A large body of water stores a more heat. Small bodies of water can be
further divided into puddles and pools. Both wiU exhibit some different characteristics.
A puddle is shallow and has a small surface area while a pool is deeper and wiU exhibit a
smaller daily temperature variations. A puddle wiU be greatly effected by shade. Both
wiU have a cooler upper surface due to heat lost by evaporation. Ice wiU form first on
small sohd objects at the surface of these small bodies and not at the banks. As the
size of the body of water increases, there is less change in the daily water temperatures
cover, and the wind velocity. Favorable conditions include low temperature, clear skies,
and low wind velocities. Since the ambient air temperature is recorded at a standard 2
meters above the ground level, the temperatures experienced at ground level generally
wiU be lower. Therefore, it is possible to have ice when the measured air temperature
Properties of Ice
Seawater is 2,700 more times abundant then fresh water. The ocean could become
nature, the conversion of saltwater to fresh water occurs regularly through evaporation
14
of freezing processes. For many years, people in the Soviet Union have collected sea ice
The properties of water and ice are the basis for the use of freezing as a separation
process. When water freezes, it forms a crystal lattice. The lattice construction process
is selective and wiU not accept substitutes for the hydrogen or oxygen ions with the
exception that fiuoride ions can be incorporated (25). Ice exists in a variety of forms,
but the majority of ice is in the polymorphic form, which is shown in Figure 6 (25).
Ice is a hydrogen-bonded compound. Each oxygen atom associates with two hydrogen
The oxygen atoms occupy the points of a hexagonal lattice in which each
oxygen atom is tetrahedraUy coordinated with four other oxygen atoms. The
0 - 0 distance is 0.267 nanometers at 0 degrees Celsius, which produces the
open low-density structure shown, (p. 21)
When water freezes slowly, pure ice can be formed. The impurities in the water will
not be included in the crystal matrix, unless the water body freezes solid or experiences
quick-freeze conditions, which can occur at temperatures less than -20 degrees Celsius
(25).
When seawater freezes, the saHnity of the ice formed averages only 4,000 parts per
million. Seawater contains between 30,000 and 35,000 parts per miUion of TDS (31).
For a given temperature, an equilibrium condition exists at which ice and brine of a
given concentration can coexist until the eutectic point of the solution is reached. The
eutectic point is the concentration at which freezing wiU not occur or at which salt
wiU precipitate before ice can be formed (12). Therefore, the salt can be incorporated
into the matrix when temperatures fall below the eutectic point. The eutectic point for
sodium chloride in seawater is -22.9 degrees Celsius (12). The freezing point of water
15
is depressed -0.062 degrees Celsius when there are 1,000 parts per miUion of sodium
chloride in a solution.
SupercooUng alone does not cause ice to form. The ice must have a site (an object
or particle) on which to form and grow. The solution must contain some centers for
The variation of the density of water with temperature is another property that
makes ice formation by passive cooling possible. Water has its maximum specific gravity
at 4 degrees Celsius. The ice formed when surface water temperature reaches the freezing
point expands and floats. Therefore, ice can be removed from the surface of the cooHng
pond.
Ice has another property exhibited when it is warmer than -15 degrees Celsius. The
contaminants trapped in the crystalline structure of the ice will slowly migrate downward
because of gravity. The combined effects of these properties make ice formation by
Sampling Ice
The procedure for ice sampling, collection, and analysis is not exact. Typically, ice
wiU vary (in a chemically) significant maimer in the vertical direction but not in the
horizontal direction (7). Cowgill adds that there is httle data available on the chemical
composition of ice from lakes and ponds. The chemical composition includes entrapped
Ice Formation
When the air temperature drops, the body of water wiU be cooled. The coldest
water will sink until the whole pond is 4 degrees Celsius. Then, as the top water layer
continues to cool, it becomes less dense. Therefore, the warmest lake water will be in
The first ice to form in a calm body of water (water velocities average less than
0.5 meters per second) consists of spicules or plate-Uke crystals. Frazil ice (disk-Uke
particles of ice less 1 millimeter in diameter) form in faster flowing bodies of water. The
small crystals that form first, grow into a network of dentries that freeze together. The
continuous cover that is formed is called skim ice. When the ice sheet becomes stable,
it continues to thicken downward (2). If the air temperature is cold enough, the latent
heat of crystallization will be conducted upward through the ice and transferred to the
air. The process of crystal growth downward in the water is called congelation, and
the ice that is formed is called congealed ice. This ice is usually made up of column-
shaped crystals with a vertical orientation. In a moving body of water, the ice needs an
The freezing point of water is essentially independent of pressure, whereas the boihng
point of water is dependent on pressure. Also, the heat absorbed by vaporization is 7.5
times the heat which is liberated at crystalization. This fact suggests that the energy
required for each pound of vapor formed will produce 7.5 pounds of ice. This concept was
Dodge shows the energy required for freezing is not directly related to the latent heat
17
requires 7.4 kilowatts per hour per 1,000 gallons while the work required in freezing is
6.3 kilowatts per hour per 1,000 gallons for an ideaUzed situation. The small difference
is energy input is insignificant when compared to the large amounts of work needed to
compensate for the irreversibifities of the freezing process (10). Snyder concurs (31):
Freezing processes have problems that are not experienced in evaporation processes.
For example, the formation of ice crystals may sometimes entrap brine. Ice crystals
must be large enough to be removed from the water, yet small enough so not to entrap
too much brine. Figure 7 shows that the purest ice formed under natural conditions,
in the Arctic Sea in a top 10-centimeter layer of ice, will occur 1 centimeter below the
surface (31). Also, the separation of ice from water is difficult. Refrigeration systems
are thermodynamically inefficient and the cost of removing heat from a unit volume of
There are many industries utflizing the of freeze-crystahzation processes for removal
ciple that ice crystals formed through freezing wiU essentially contain pure water (6).
The resultant ice can be removed, washed, and melted. Conversely, the concentrated
18
brine may be recycled for reuse in some industries. Two different industrial freeze tech-
nologies have been developed in the 1980's (11); the Vacuum Freezing Multiple Phase
Transformation (VFMPT) and the Indirect Freeze Concentration (IFC) process. These
processes can operate in situations where TDS concentrations range from low to high
and they are easy to scale-up from the bench-scale test to the prototype unit. The equip-
ment used in these processes is relatively insensitive to fouhng. The equipment costs
less than evaporation equipment. Since the latent heat of fusion is less than the latent
Also, the influent streams to the systems do not typically require pretreatment. These
advantages also decrease the operation and maintenance costs. Individual systems have
been tailored to require less energy but freezing processes stiU remain energy intensive
VFMPT Process
The VFMPT (by Calyxes) process utihzes vacuum freezing. Both the ice and the
vapor formed at the triple point axe used. The vapor provides a means for melting
the washed ice crystals (6). The VFMPT process is effective, rehable, and efficient.
This process is achieved by a Sub-Triple Point Vapor Processing Unit (STPVPU) and
hquifying the vapor in the STPVPU and then melting and washing the crystals in the
ICWM (6). VFMPT claims to have the first commercially available freeze-crystahzation
system. This process has advantages over both reverse osmosis (RO) and evaporation
processes. VFMPT can concentrate solutions to their eutectic point whereas RO can
only concentrate up to 7 or 8 percent of the solutions eutectic point. This system has
19
a longer Ufe than RO systems and is not as sensitive to fouhng or scale formation. It
can handle either acidic or basic solutions and also solutions containing oxidizing agents
while RO can not. Also, this system is not as sensitive to corrosion problems as RO or
evaporation equipment.
so that the ice will subhmate or go directly from a sohd to a vapor at a lower-than-
Figure 9 shows a phase diagram which explauis the operation of the devices (6).
IFC Process
metaUic barrier from a fiowing brine solution while coohng and partially freezing the
brine. In the IFC system, ice crystals are formed in the bulk of the hquid without growth
Figure 10 shows the IFC process, which has a freeze-exchanger that produces ice
crystals; a wash column for separating and washing the crystals; a precipitate separa-
tion device for growing and separating precipitate crystals; and a refrigeration system.
The low temperature minimizes metaflic corrosion and allows the use of favorable con-
struction materials. The low temperature also helps enhance precipitation because most
substances are less soluble at lower temperatures. No chemicals are added so the total
volume of waste for ultimate disposal is minimized. The system is adaptable to different
not contaminated by the waste because a closed indirect system is used. No air pollution
Apphcations
dustries include mining, orange juice manufacturuig, pickhng, industrial waste con-
Summary
The combination of shade, the temperature regime near the ground, and winter
conditions make passive ice formation a process of the future. The temperatures in
shaded areas wiU be several degrees cooler than the temperatures recorded in the sunny
locations. Shade prevents a portion of the sun's radiation from reaching the water.
Birge reported that the primary factor in melting is the impact of radiant heat on the
ice (18). A decrease in the radiation will help prevent ice melt and keep water without
The temperature at ground level will add to this effect. Temperature measurements
wiU be cooler than the official recorded temperature since the ambient air temperature
is recorded at a standard 2 meters above the ground level. In the winter, ground-level
air temperatures wiU be cooler. The benefits offered by shade and lower temperatures
21
show that the freezing of water is possible even when the official recorded temperature
is above freezing and thus enhance the use of passive coohng ice-makers.
Locating the ice-maker system away from the city environment will also increase the
amount of ice produced. In the city, the houses, large office buildings, and factories form
an irregular surface that slows air movements. These structures will absorb more heat
during the day than the features found in country. At night, this heat wiU be retained
for a longer period than it would be in a country area. Added to the surface irregularities
is an increase in airborne paxticulates, which also retain heat. This combination results
in the formation of a heat island that concentrates heat in the center of the city. By
optimizing the cooler conditions offered by shaded locations, ground level conditions,
PROCEDURES
This chapter presents a discussion of the methods and procedures used to accomphsh
the objectives of this study. The tests utihzed include experimental runs conducted
outside under ambient conditions and a second set of rims conducted under controlled
conditions.
Approach
The experiments were conducted to simulate conditions similax to those used for
ice formation processes in Iran (3). A series of tests were run in late winter (February
and Maxch 1989) to determine if a significant amount of ice would form in the ambi-
ent environment for various concentrations of sodium chloride (NaCl) in pure water.
The amount of ice formed would be a function of the temperature and time. Other
tests were run in a controlled temperature environment (a freezer unit) to compare the
amounts of ice formed in the unit to the amounts of ice formed under varying ambient
conditions. The tests under the controlled conditions would also show how much time is
required to form a significant amount of ice and the quahty of the ice formed. Infiuent
NaCl concentrations were varied to determine the effect on the effluent quahty. Lastly,
Stephan's equation was used to estimate how much ice should form under both the
ambient and controlled conditions of the experiment. This estimate was used in the
economic analysis.
22
23
Outdoor Tests
The plan was to simulate and test the procedures used in the Iranian passive ice-
maker. Water with different concentrations of NaCl was placed in shallow insulated pans
records both humidity and temperature, was used to monitor the temperature of the
shaded location. The ice was to be harvested periodically and the inches of ice formed
during the interval were recorded. Next, the ice would be washed to remove residual
brine. Then, the ice would be melted at room temperature and the melted volume
recorded. Samples of the ice collected would be analyzed with an ion chromatograph
The concentrations of the NaCl to be used were determined chemically. Since sodium
weighs 22.99 miUigrams per mole and chlorine weighs 35.45 miUigrams per mole, NaCl
weighs 58.44 milhgrams per mole. Therefore, sodium chloride is 39.34 percent sodium.
The milhgrams per hter of sodium in solution were determined by dividing the weight of
sodium chloride in the solution by the percent of sodium in the compound (15). Table
midity, wind, time, volume, and solution concentration. Temperature and time were
tor. Due to evaporation, precipitation, and other weather related incidents, the solute
concentration probably varied. The solvent volume was selected as a control, but flocks
of birds drank the less concentrated samples. Therefore, the controls were not able to
be controUed.
24
Freezing experiments were conducted inside an upright freezer unit. Insulated cups
were placed inside the freezer and fiUed with the test solution. The temperature in the
used to monitor the temperature in the freezer and the freezmg time interval. At the
end of the freezing time period, the ice which had formed was removed and washed. The
volumes of ice and unfrozen solution from each cup were measured. An IC was used to
measure the sodium concentration in the melted ice and in the brine solutions coUected
at the end of the freezing period. The amount of ice lost during the harvest and washing
phase could be found using a mass balance on the initial and final volumes of the test
solutions. The mass balance also required values for the concentrations of sodium in
the ice formed and in the residual brine. The amount of usable ice compared to the
total amount ice formed was also determined by differences in weight. The results
obtained from this phase would be used for comparison against the results obtained
After the preliminary freezer experiments, it was determined that additional factors
needed to be controUed to provide statisticaUy vahd results. Each bucket used in the
tests was fiUed with 33 pounds of sifted sand. The time in the freezer was accurately
monitored so that each run was 7 hours long. The experiments were switched from a
frost-free freezer unit which varied over a 30-degree Fahrenheit temperature range to a
non-frost-free freezer unit which exhibited a lower range of temperature variation (12.6
degrees Fahrenheit).
25
Each test run concurrently used solutions at the three test concentrations in order
that a representative solute concentration would experience the same conditions in each
run. DistiUed water was used to mix the solutions used the experiments. The infiuent
water was first treated by reverse osmosis. Then, the water was sent through the
Barnstead stiU which is used for distiUation in the environmental lab. The water was of
a good quality and checks were run for verification. Only trace amounts of sodium, on
the order of 1 part per imlhon, were found in the effluent water. Each of the three cups
fiUed with 500 miUUiters of one of the test solutions. The first cup had 500 miUigrams
per hter of sodium; the second had 1,500; and the third had 4,500. The cups containmg
solution were placed in cups in the buckets, surroimded by sand, and frozen for 7 hours.
The cups in the bucket were used to keep the amount of sand in each bucket consistent
for each run. Figure 11 depicts the configuration of the test unit. Ice formed by the
end of the test period was removed from each solution cup and weighed before and after
washing.
The variables of interest in each test run were both the final salt concentrations in
the ice formed and in the unfrozen solution left in the test cups. Samples of melted
ice and residual brine were tested by an IC to determine the sodium concentration in
the samples. The influent concentration was controUed by applying the protocol set in
Test Facihty
The roof of the Texas Tech University CivU Engineering BuUding was the site for
the outdoor phase of the experunents. Shade was provided by a wooden wall set up
26
on the south side of the experimental area. The pans in which the test solutions were
The ice removed from the test vessel was taken to the lab where it was washed
using a strainer and then melted. The volume of melted ice was measured in volumetric
beakers.
This phase was conducted using an upright freezer unit located in the Environmental
Science Laboratory in the CivU Engineering Department at Texas Tech University. The
washing and measuring of the ice utihzed the same procedures and facUities as the
outdoor phase. The test solutions were prepared the same maimer.
The test solutions used in the experiments were prepared in the lab by adding sodium
weighing the salt, used for each of the three test concentrations.
and ionic separation abiUties. A filtered 100-microhter sample of hquid is injected into
the IC and is pumped through ion exchange resins where the cations are sepaxated.
Vaxious ions have paxticulax affinities for the resin and the ions in the test solution can
be identified by the rate at which they migrate through the IC column. An ion's affinity
is largely a function of its size and valence. After migration, the ions axe neutraUzed
and sample ions are converted to thek corresponding strong base. The alkahnity is then
are output by a printer on graph paper. The peak heights are then measured and
calibrated. Cahbration curves formed from standards run through the IC are used to
27
interpret sample results. Typically, five different standards with known values of the
Data Analysis
Data was coUected ui different phases. The first phase mvolved an outdoor ex-
periment and was used to help develop a plan for scaling-up the passive cooling-pond
concept. The second phase, which was used to develop the procedure for the final phase,
involved indoor testing in a freezer. The third phase involved a controUed freezer exper-
iment. The results of this phase were used to determine the quahty of effluent predicted
This phase involved tests conducted outside during the months of February and
March 1989. Many problems were experienced in this phase. Equipment had to be
developed and an outdoor location for experiment found. The roof of the Texas Tech
CivU Engineering Building was chosen because it was close to the lab and because access
to the site was controUed. People and four-legged animals were denied access to the
experimental units. However, birds were a problem. They drank water from the control
unit and from some of the units that contained the lower NaCl concentrations.
Some problems were anticipated. Passive cooling is whoUy dependent on the local
chmatic conditions and the freezing conditions might be sporadic in occurrence. There
was the logistical problem of transporting the water to the roof and the ice to the
laboratory. People and carts were sohcited to help move both the water and ice. To
duphcate the Iranian-type coohng pond method being investigated, shade had to be
28
provided, for this phase. The shade was provided by modifying plywood frames found
on the roof which were left from a previous experiment. The temperature in the shade
Operational problems developed during this phase. The test solutions froze to sohd
ice in the experimental units. An extreme cold period was experienced and the test
solution in aU the units and the control froze sohd in a few hours time.
Another problem was that the NaCl test concentrations were approaching seawater
levels. In the smaU volumes, there was limited reservoir space in the experimental unit
for these soUds to migrate to the brine supply when ice crystals formed. In the extreme
temperatures experienced, the smaU volumes of the test solutions froze too quickly for
Houses, laxge office buildings, factories, and landscaping vegetation in the city form
an irregulax surface that slows air movement. Structures and paved surfaces wiU absorb
more heat during the day than land mass in the country. At night, this heat wiU be
retained for a longer period than in a rural area. Added to the surface irregularities are
the increases in airborne particulates in the city that also retain heat. The result is the
formation of a heat island which concentrates heat in the center of the city. AdditionaUy,
the air temperature experienced at ground level during the night hours is lower than
the layers of air above it. Less ice could have been formed because the experiment was
located on a roof in the center of Lubbock, Texas. The test units may have gained heat
The test unit was a bucket in which three cups were placed. The cups were then
insulated by placing soil in the voids between them. The cups were fiUed with 500
miUihters of solution and placed in a freezer until sufficient ice formed. A sketch of the
The soil used as insulation for the cups was not uniform and better insulation may have
been offered to one part of the container when compared to another area. The amount
of soil used also varied shghtly with each run. The freezer initially used was frost-free.
Therefore, the temperature varied more than 20 degrees Fahrenheit during the test
period. The time the solutions were left inside the freezer had to be varied in order
to get enough ice for the test run. Three different concentrations of NaCl were used.
Each run used three samples of the same concentration in the test unit. The freezer
conditions experienced by one run could vary for another run which make comparisons
Modifications to the previous tests included the provision of a more uniform insula-
tion, a different freezer, and more precise procedures. The sand used for insiUation was
sieved and weighed before placement in the test unit. The freezer unit used was not
frost-free and did not have as high a cychc temperature variation as the unit used in the
second phase. The tests were run for a specified time period (7 hours) which aUowed
Stephan's equation was used to estimate how much ice would form under the different
conditions of the experiment and to predict how much ice would form in a typical winter
season in Lubbock, Texas. By inputting the constants into Stephan's equation it can
be simphfied to (2):
h = 0.035S°-^a (3.1)
where h is the thickness of the ice in meters, S is the summation of the number of
degree-hours of freezing, and a is a correction factor less than 1 (2). This equation wiU
be apphed to both the outdoor and controUed test phases. Although, the equation only
describes ice growth after ice formation, its use wiU help describe how much ice can be
formed if a conservative value is used for a. The limitations of the Stephan equation
RESULTS
This chapter is organized into three different sections-data presentation of the ice
making tests; ice development using Stephan's equation for analysis; and an economic
analysis of several ice-making techniques. The results of the ice-making techniques wiU
Data Presentation
Tables 2, 3, and 4 present the results obtained in this phase. Table 2 shows the
nights which were below freezing during the 1988-89 winter period. Each date is fol-
lowed by the average temperature below freezing (ATBF) in degrees Fahrenheit and its
duration. This data was obtained from NOAA records for the winter 1988-89 period in
Lubbock, Texas. The ATBF along with the duration of freezing weather for each day
was used to calculate the degree-hours of freezing experienced in the 1988-89 winter
period for Lubbock. This value wiU be used in Stephan's equation. The temperature
experienced in an instrument shelter 2 meters off the ground may be shghtly warmer
than temperatures at ground level, so the value of ice predicted by Stephan's equation
wiU be conservative.
Table 3 shows the days on which data coUection was attempted. Days in the time
interval which are not hsted between these dates are periods in which no data was
collected because ice was not formed on the building roof. Some of the days shown in
Table 2 did not have the cold persist long enough for ice to form in the saline solutions.
31
32
The results from the outdoor tests shown in Table 4 are highly variable. This fact
may be due in part to the variation in the ice coUection procedure used on some days
during the study interval shown in Table 4. The ice in the comers of the pans was so
thick that the the ice could not be removed with a hammer. Therefore, the ice in the
middle of the test unit was coUected. By the end of the winter, the ice in the comers of
the test unit had buUt up significantly. During mUder temperature periods, the corner
ice was coUected and mixed with the ice coUected from the center. The corner ice could
have been of better quality than the new ice formed at the center of the unit since the
NaCl trapped in the ice interstices wiU migrate slowly downward due to gravity.
Another factor is the possibUity that as the experiment continued, a residual build-
up of salt formed in the containers. In the rush to get off the roof and out of the cold,
the pans were not washed thoroughly after each run which could have added to the salt
buUdup. Variations in temperature could also cause the results to vary. A colder day
wiU freeze the water more quickly and thus entrap more dissolved sohds.
This phase of the experiment was used as a prehminary test procedure to design
the final experiment. The major problems experienced in this part of the experiment
was the identification of a large number of variables which needed to be controUed both
during the freezing interval and in the analysis phase. Evidence of the high variabihty
is shown in the Table 5. The lower NaCl concentrations were not impacted by these
variables in the test procedures as much as the higher concentrations. The standard
deviation for the 4500 milhgrams per hter solution is over 50 percent of the mean.
in Chapter 3. The revised procedures were used in order to make the results vahd and
worthwhile.
This was the fmal laboratory phase of the experhnent. Tables 6, 7, and 8 show the
results from the 500 miUigram per hter, 1,500 miUigram per hter, and 4,500 mUligram
per hter test concentrations of NaCl, respectively. Each table also shows the mean,
standard deviation, maximum, minimum, and coefficient of variation for the different
concentrations. The graphs of the results axe shown in Figures 12, 13, and 14. The
graphs show NaCl concentration in the ice and in the residual brine solution.
The coefficients of variabihty displayed in Tables 6, 7, and 8 show that the results are
good statisticaUy and that the modifications made in the test protocol were beneficial.
The results varied shghtly because the freezer exhibited a 12.6-degree Fahrenheit range
during its operational cycle. The cycle period lasted approximately 30 minutes. Another
cause of vaxiation may have been the sand used for insulation. The sand was sieved and
weighed in each bucket, but it was not homogeneous. Vaxiations in the sand mixture
from one test unit to the preparation of another also contributed to the variabihty.
The results from the 500 miUigrams per hter run had three outhers. The outUers were
a result of poor laboratory procedures. The samples were stored over a weekend and not
The outhers were not used to calculate the results from this run. The outUers test showed
that the discarded runs had NaCl concentrations that were approximately greater than
The 1,500 and 4,500 miUigrams per hter runs exhibited lower coefficients of variabU-
ity than the 500 miUigram per hter. These numbers show that the runs are repeatable
and StatisticaUy vahd. When the three mns are graphed together a curve (Figure 15)
can be drawn showing the removal rate for the conditions used. More runs would help
vahdate this curve. However, it does show an interesting possibUity. The equation of
the curve has a correlation coefficient of 1 for a third-order polynomial equation of the
When seawater freezes, the ice has an average of 4,000 miUigrams per hter of sahnity,
while the water itself contains 33,000 miUigrams per hter (31). Seawater frozen naturaUy
in the arctic can be added as shown in Figure 16. The correlation coefficient is 1 for
a third-order polynomial equation. Further studies in this area could help vahdate an
equation for the concentration of dissolved sohds in ice when natural, pond-hke freezing
occurs.
The results show that an effluent of significant better quahty can be obtained in
ice formed under pond-hke freezing conditions. Dissolved sohds can be trapped in the
interstices of the frazil ice as it forms a sheet. Therefore, a passive freezing system
operated to produce ice wUl be productive and feasible if the system can be operated
at a low cost.
Calculations showed that an average of 70.4 miUihters of ice was lost in the washing
step. This value was approximately 50 percent of the ice formed. Since the ice is not
as pure as it is in the energy intensive, industrial methods, washing does not have a
Using the simplification of Stephan's equation presented in Chapter 3 and the degree-
days of freezing for the winter of 1988-89 in Lubbock, Texas, the amoimt of ice expected
to form is 2.22 inches over a night. This value was calculated for an S of 7.55 degree
hours, where degrees are in Celsius units. The value of S is for an average period of 90
nights of freezing in Lubbock, Texas. A value of 0.58 was used for a. This value was
chosen to malce the economic estimate conservative. The value of 2.22 inches is used in
The temperature used to calculate the amount of ice that was expected to form, was
taken from NOAA records. This temperature was recorded in an instrument shelter
at an exposed location (sunny during clear-daytime conditions) and above the ground.
The shade provided for the passive cooling ice-maker system would lower the effective
temperature experienced by the ponds during daytime hours. The difference between
the recorded temperature and the actual temperature near the ground would also cause
lower temperatures to be experienced by the ponds. Therefore, more ice would form
When Stephan's equation was apphed to the controUed condition tests conducted in
a freezer unit, 3 inches of ice were expected to form. In actuaUty, only an average 0.75
inches formed. The value of S calculated from an average temperature in the freezer
imit of -15.3 degrees Celsius and a time of 7 hours, was found to be 4.46 degree-days.
Therefore, the value of a would be 0.25 for the freezer unit. The value of a is low
because Stephan's equation only considers heat lost by conduction after the ice sheet
is formed. Another factor that could have affected the value was that the soU used for
insulation was at room temperature when it was placed in the freezer, and therefore
36
exerted a coohng capacity. The smaU diameter of the freezing units (cups) and the
higher temperature of the freezer waUs compared to the heat sink of the sky could have
Economic Analysis
prehminary estimate was used to evaluate the capital and operational costs in order
to compare this method to the energy-mtensive methods exhibited by the IFC and
V F M P T systems. By comparing the costs of the three different systems, the value of
the passive coohng system as a method of pretreatment can be estimated. Table 9 shows
The design provides a 3.5-foot water depth in the pond. The volume of water input
can be modified to optimize the amount of ice formed by applying Stephan's equation
and using the local weather forecast for the next 24-hour period. Using this method for
the 1988-89 winter period, the average amount of ice formed in Lubbock is 2.22 inches
per night. To prevent the water from freezing sohd and to form ice of a good quahty, a
depth of three times the depth of ice formed should be used. The 4-foot deep pond wiU
The design shows that two sides of the concrete pond are sloped. The sloped sides
provide an access for vehicles which wiU remove the ice. In the morning, the remaining
brine wiU be drained. The ice sheet wiU be broken and the ice wiU be moved by a
tractor equipped with a blade attachment to the melting pond. Grit picked up by the
ice during formation and removal can be settled out later in a clarifier.
37
The capitol cost estimated for the passive coohng pond system includes cost of ex-
cavation; concrete form-work, pouring, curing, finishing, and materials; a pipe network
system with two low capacity pumps per pond, and a smaU tractor with a plow at-
tachment. As shown in Figure 17, there is no shade provided for the melting pond,
so melting wiU be encouraged by radiation. Therefore, energy wiU not be needed for
The waste water to be treated can be stored in ponds until processed. The only
energy required wUl be the fuel for the ice-removal vehicle and the electricity for the
water pumps. The power used by the pumps can be minimized by utihzing a smaU
slope in the ponds. This slope wiU faciUtate the drainage of the brine remaining after
ice formation. Other operational costs include the wage of the ice-removal vehicle driver
and vehicle maintenance costs. This economic analysis shows the cost to add the passive
sohds. Therefore, human factors for system operation needed are already in place and
The final cost per gaUon produced is based on 90 days of freezing weather and an
ice production amount of 50,000 gaUons per night. These values are based on data for
weather per year according to NOAA records. The surface area required to produce
50,000 gaUons of ice (based on an average 2.22 inches forming per night) may be provided
The two freeze technologies examined axe the IFC system and the V F M P T system.
Tables 10 and 11 show the cost analyses for these processes. The data shown in these
tables is the only data which was avaUable on the costs (6, 11).
38
The cost of the IFC system is based on 8000 hours of operation per year and a flow
of 300-500 gaUons per minute. The IFC system produces water at a cost of 2 cents per
gaUon based on 1987 doUar values. The VFMPT system produces 50,000 gaUons per
day and the cost per gaUon is 0.31 cents adjusted to 1987 values. The passive coohng
ice-maker is comparable to the V F M P T in cost and production. The cost per gaUon
is 0.37 cents based on 1987 doUars for the same water production quantity. The IFC
system produces ten times the amount of the other systems and costs almost ten times
The passive coohng ice-maker system wiU not be as influenced by rising energy costs
as the other two systems, since the only energy input is for the ice-removal vehicle
and the pumps. The costs of the system wiU decrease as the system is moved to higher
latitudes or altitudes. More ice can be produced naturaUy for the same costs. Therefore,
the passive coohng system could be a reasonable pretreatment system for the removal
of dissolved sohds.
CHAPTER 5
CONCLUSION
1. The data gathexed fox the thiee diffexent test concentxations show that
systems. In no case did the ice that foxmed contain moxe than 50 pexcent
Lubbock, Texas.
quahty.
xemoving dissolved sohds from watex in Lubbock, Texas, if enexgy pxices xise.
Recommendations
3. Study the use of metal frames to potentiaUy increase heat loss and
39
40
of ice formed.
k
BIBLIOGRAPHY
1. Anderson, Bruce and Malcom WeUs. Passive Solar Energy: The Homeown-
er^s Guide to Natural Heating and CooHng. Andover, Massachusetts: Brick-
house PubHshing Co., 1981.
2. Ashton, George D. Ed. River and Lake Ice Engineering. Littleton, Col-
orado: Water Resources Publications, 1986.
10. Dodge, Barnett F. "Fresh Water From Saline Water: An Engineering Re-
search Problem." In American Scientist. Vol. 48, No. 4, December, 1960,
pp. 476-513.
41
42
13. Fynn, R. Peter and Ted H. Short. The Salt StabiHzed Solar Pond For Space
Heating -A Practical Manual-. Wooster, Ohio: The Ohio State University
Agricultural Research and Development Center.
14. Geiger, Rudolf. Scripta Technica, Inc. Trans. The Climate Near the Ground.
Cambridge, Massachusetts: Harvard University Press, 1965.
16. Hanson, David G. and John I. Yellott. A Study of Natural Cooling Processes
In A Hot, Arid Region. Philadelphia, Pennsylvania: University of Pennsyl-
vania, 1978.
19. "J D Observer." IlHnois: John Deere Company, Summer 1989, pp. 5-20.
20. Jumikis, Alfred R. Soil Mechanics. Princeton, New Jersey: D. Van Nos-
trand Company, Inc., 1962.
21. Labine, R. A., ed. "Making Fresh Water From Salt Water."
Chemical Engineering. June 13, 1960, pp. 152-155.
24- Passive Solar Design Handbook. New York: Van Nostrand Reinhold Com-
pany, 1984.
25. Pounder, Elton R. The Physics of Ice. Oxford: Pergamon Press, 1965.
30. Simpson, Charles. "Freezing the Salt Out of Sea Water." Engineering. April
24, 1970, p. 418.
33. Texas Solar Realities, How to Build with Solar Power. Texas: Governor's
Office of Energy Resources, 1979.
37. Viessman, Warren, Jr. and Claire Welty. Water Management Technology and
Institutions. New York: Harper and Row Publishers, 1985.
45
46
Process Location
FREcZING MELTING
CHAMBER UNIT
HEAT EXCHANGER
BPfNE RETURN
0 0.01
Temperature
SEA-WATER SALINITY^
oc 3
1 4
^-
"Z
UI
o 5
UJ
U
u. *•
oc
§,
Z
&9
O
1 2 3 4
SAUNITY (PER CENT)
4 Slurry
•[^-^Vacuum^
Flrwt
Vapor
'i^r'aezing" (Cryotala and Ue(h«r Liquor)
1
Crystal
Washing
Second
-+-J'Two Stage
First
Vapor
Second
Soeond
Vapor T Purlflod
Oryolafi
Figure 8. V F M P T Process
Source: (6)
54
/WWAA
BfBNE
PMCCtPrrATE SEPARATOR
Table 1
^* « •
>
°o°
Figure 11. Test Unit
58
Table 2
Table 3
Date Significance
Table 4
Winter Results
Table 5
Prehminary Results
Table 6
1 40.53 617.08
2 87.59 500.27
3 50.61 580.57
4 50.61 540.42
5 53.97 503.92
6 87.59 522.17
7 77.50 503.92
8 53.97 609.78
9 74.14 591.52
10 43.89 562.32
11 57.33 511.22
12 60.70 598.82
13 80.87 628.03
14 60.70 562.32
15 80.87 624.38
16 106.03 573.27
17 65.88 595.17
Table 7
1 464.09 1785.17
I. 309.45 1639.16
3 427.11 1675.66
4 359.88 1449.34
5 487.62 1697.56
6 541.40 1617.26
7 343.07 1540.60
8 423.75 1726.77
9 393.49 1686.61
10 373.32 1898.33
11 470.81 1825.33
12 504.43 1781.52
13 443.92 1792.47
14 544.77 1828.98
15 638.89 2146.55
16 975.05 2237.81
17 477.53 1770.57
18 538.04 2007.84
19 576.92 1777.87
20 606.12 2131.95
Table 8
1 1311.21 5037.59
2 1243.98 4782.07
3 941.44 3778.24
4 891.01 3102.93
5 2084.38 7191.27
6 1580.14 5220.10
7 1546.52 5366.12
8 1731.41 5147.10
9 1966.72 6515.96
10 1580.14 5731.15
11 1657.46 3471.61
12 1563.33 5785.90
13 1630.56 6059.67
14 1731.41 5731.15
15 2689.47 7519.79
16 2151.61 6132.68
17 1512.91 5512.13
18 1865.88 6424.70
19 1630.56 6077.92
20 1983.53 6023.17
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I . ^Bx Hx_ / ^IN ^H /
H ' H'' S
^H * 4
^H /
p. H x ji \ ^
L' H''
p. H x
2000 n
1000-
c
•
o
c
o
o
5000-1
4000-
3000-
o 2000-
c
o
O
1000-
Plonwlow:
Section A-A:
•VT/'W^jj, <ffT77T'
^^7F> 276"
J 12' .' 12 > 16- 12*
Table 9
(1987 doUars)
Item Cost
Table 10
Table 11
that the Library and my major department shall make it freely avail-
further written permission and that any user may be liable for copy-
right infringement.
Date Date
I,, I, •f'sjK^ '•v. 1