Europaisches Patentamt

European Patent Office

J) Publication number: 3 434 207 A 2
Dffice europeen des brevets

© EUROPEAN PATENT APPLICATION

© Application number: 90312449.3 © Int. CI.5: G01N 9/00, G01 F 1 7 / 0 0

© Date of filing: 15.11.90

The title of the invention has been amended © Applicant: MICROMERITICS INSTRUMENT
(Guidelines for Examination in the EPO, A-lll, CORPORATION
7.3). One Micromeritics Drive
Norcross Georgia 30093(US)
© Priority: 17.11.89 US 438752
© Inventor: Orr, Clyde, Jr., Dr.
© Date of publication of application: 5091 Hidden Branches Circle
26.06.91 Bulletin 91/26 Dunwoody, Georgia 30338(US)
Inventor: Camp, Ronnie W.
® Designated Contracting States: 3001 Bunten Road
AT BE CH DE DK ES FR GB GR IT LI LU NL SE Duluth, Georgia 30136(US)
Inventor: Gibson, Kathryn Hill
533 Milligan Drive
Stone Mountain, Georgia 30083(US)
Inventor: Hendrix, Warren P.
1535 Alcovy Road
Lawrenceville, Georgia(US)

© Representative: Chettle, Adrian John et al

Withers & Rogers 4, Dyer's Buildings
Holbom London EC1N 2JT(GB)

© Gas pressure comparison pycnometer.

© A gas comparison pycnometer is disclosed

which provides a method and apparatus for deter-
mining and checking the accuracy of the volume of
a solid substice. The pycnometer is also outfitted
with a unique cap assembly (15) which fixes the
volume in the pycnometer's sample chamber (20)
from run to run, and a flow limiting system (33, 35)
^
<
^ to prevent entrainment of fine sample particles in the
gas stream without prolonging the analysis. The pyc-
^PS nometer also employs a series of purges with a
suitable gas to carry unwanted moisture and vapors
out of the system. This pycnometer solves many
3 problems in the prior art by quickly and accurately
CO
determining the volume of a solid substance.

Q.
UJ

Xerox Copy Centre

 1 EP 0 434 207 A2 2

GAS COMPARISON PYCNOMETER

Field of the Invention chamber greatly decreases the accuracy of the

volume determination.
The present invention relates to an apparatus Fourth, problems arise when the sample is
for measuring the volume of a solid substance ad placed into the pycnometer. The sample may be at
more particularly to a pycnometer which has an 5 a temperature different from the pycnometer. Also,
automatic purging and run control system. unwanted moisture and vapors enter the system
when the sample is introduced into the pycno-
Background of the Invention meter. The sample may itself contain large quan-
tities of vapors which will cause the pressures to
The density of a substance, its mass divided w vary from the ideal values. These foreign vapors
by its volume, can be an identification parameter must be removed before a precise volume mea-
for pure substances, a composition descriptor for surement can be achieved. Heretofore, unwanted
mixtures of two pure substances, an indicator of moisture and vapors have been removed from the
adulterations in preparations of otherwise known pycnometer by attempting to completely evacuate
composition and a detector of voids in an appar- w the system with a vacuum pump. Other devices
ently solid object. remove the unwanted moisture and vapors by a
Density must be accurately determined to pro- prolonged flushing of the system with a steady,
vide the above information. The mass of a solid slow flow of helium. Other devices try to purge the
substance is easily and accurately determined with system by manually alternatively increasing and
modem analytical balances, and volume is also 20 decreasing the gas pressure in the sample cham-
easily and accurately established for solid sub- ber.
stances of uniform geometric shape such as Fifth, expansion passageways have included
spheres and cubes. However, volume of irregularly- devices to restrict the rate at which expansion of
shaped solids such as minerals, commodities and gas occurs from one chamber to the other during
many other substances of commercial significance, 25 analysis. This has been necessary to prevent fine
is not easily calculated. powder particles of the sample from being en-
Commercially available gas comparison pyc- trained in the gas flow, which would lead to loss of
nometers typically measure volumes of 50 cm3 to a sample quantity and fouling of other system com-
precision of ± 0.1 cm3. Greater precision is sorely ponents. However, restricted expansion flow be-
needed if the measured density is to function as an 30 comes particularly slow as equilibrium is approach-
identification parameter, a composition descriptor, ed between the two chambers, prolonging the time
an indicator of adulterations or a detector of voids. required to complete an analysis.
As is well known, such pycnometers operate by The above deficiencies can greatly affect the
pressurizing gas around a sample in a chamber, accuracy of the volume calculated by the pyc-
measuring the pressure, allowing expansion of the 35 nometer. However, no prior art pycnometers have a
gas into an additional chamber, and measuring the way to check the precision of its volume deter-
pressure in the combined volume. The result is mination. Thus, there has been a need in the art for
compared to calibration data to determine the vol- an apparatus exhibiting greater precision and effi-
ume of the unknown sample. ciency when determining the density of a solid
Current gas comparison pycnometers suffer 40 substance.
from many deficiencies which limit the precision of
the volume determination. First, the devices are not Summary of the Invention
stable against ambient temperature variations. Any
change in room temperature can influence the The present invention solves the above prob-
pressure measured in either the sample chamber 45 lems in the art by providing a pycnometer which
or the expansion chamber. can quickly and accurately determine the volume
Second, when an expansion is made from the and density of a solid substance.
sample chamber into the expansion chamber, an Generally described, one aspect of the present
internal gas energy change transpires. Its influence invention provides an apparatus and method for
cannot be accounted for except by insuring that the so determining and checking the accuracy of the vol-
pressure change encompasses identical limits. ume of a substance. The sample to be tested is
Third, closure devices for the sample chamber placed in a sample chamber with a fixed volume
do not adequately seal and reproducibly define the and a sequence of tests is carried out, monitored
chamber to insure a constant volume when the and compared until the results are within a set
tests are run. An inadequate closure of the sample tolerance of being a constant value. Only then is

2
 i EP 0 434 207 A2

this constant value accepted as the volume of the the flow of gas during expansion from one cnamoer
sample being tested. When it is determined that to the other is restricted to prevent entraiument of
the volume reading is accurate, this volume is then fine powder particles in the flowing gas, until the
used to calculate the density of the substance pressure in the source chamber drops to a safe
being tested. 5 level at which entrainment is not a problem. At this
In the preferred embodiment, a microprocessor pressure level, the flow restriction is ended, so that
controls performance of a sequence of test runs the gas can complete its expansion more rapidly
which provide the progression of results to the than possible when flow is restricted.
constant volume. The sample chamber is pressur- Thus, it is an object of the present invention to
ized with a gas such as helium, and the pressure w provide an apparatus which can accurately deter-
transducer measures the pressure in the sample mine the volume of a solid substance.
chamber. The gas is then allowed to expand into It is a further object of the present invention to
the expansion chamber and the pressure is mea- provide an apparatus which can transfer gas to or
sured in the connected chambers. In the alter- from a sample chamber quickly without entraining
native, the expansion chamber may be pressurized 75 sample powder in the gas stream.
with helium and the gas then allowed to expand It is a further object of the present invention to
into the sample chamber. The volume of the solid provide an apparatus which can accurately deter-
sample is calculated and stored. The sample and mine the density of a solid substance.
expansion chambers are then vented to atmo- It is a further object of the present invention to
sphere, and the above steps are repeated a pre- 20 provide an apparatus which can purge unwanted
determined number of times. The volume of the moisture and vapors quickly and efficiently from a
last run is compared to the volume of previous pycnometer.
runs. If these volume comparisons or volume de- It is another object of the present invention to
viations are within a predetermined tolerance, un- provide a pycnometer which can check the accu-
contaminated helium has been established in the 25 racy of its volume determination.
system and any temperature discrepancy between It is a further object of the present invention to
the sample and the system also has been dis- provide a pycnometer apparatus with a closure
sipated. The volume of the last run is accepted as device which can assure the same constant volume
accurate and used for the density calculation. If the each time the closure device is engaged in a
volume deviation is greater than the volume toler- 30 sealing arrangement.
ance, test runs are repeated until the volume de- Other objects and advantages of the present
viation over the final runs is less than the volume invention will become more readily apparent from
tolerance, or until: initially specified number of runs the following description of a preferred embodimen.
has been reached.
According to another aspect of the invention, 35 Brief Description of the Drawing
the volume of the sample chamber remains fixed Pig. 1 is a pictorial- view of the pycnometer
from run to run because of a unique closure device apparatus embodying the present invention.
or cap assembly sealing the sample chamber. The Fig. 2 is a vertical cross-sectional view taken
cap assembly described above includes a rigid along line 2-2 of Fig.1.
portion which engages the sample chamber to al- 40 Fig. 3 is a cross-sectional view taken along line
ways define the same volume within the chamber. 3-3 of Fig.
Mounted in the cap is a compressible gasket mem- Fig. 4 is arear view of the apparatus of Fig. 1.
ber. When the cap is inserted into the opening of Fig. 5 is a schematic representation of the pneu-
the sample chamber, the gasket compresses matic and electrical circuits associated with the
against a continuous surface surrounding the open- 45 pycnometer shown in Fig. 1.
ing of the sample chamber and insures a tight Fig. 6 is a pictorial view of the preferred em-
fitting sealing arrangement. bodiment of the cap assembly.
Another aspect of the present invention pro- Fig. 7 is an exploded view of the elements of
vides an improved method for purging the pyc- the cap assembly of Fig. 6.
nometer system of unwanted moisture and vapors. so Fig. 8 is a side plan view of the ramp shown in
This purging includes a particular routine for re- Fig. 9.
peatedly pressurizing the sample chamber and the Fig. 9 is a schematic flow diagram of the overall
expansion chamber above atmosphere and then operation of the pycnometer.
venting these chambers back to atmosphere. This Fig. 10 is a schematic flow diagram of the fill
method of purging provides a more efficient way to 55 sequence utilized in the operation of the present
remove unwanted gas than prior continuous flow invention.
methods. Fig. 11 is a schematic flow diagram of the
According to another aspect of the invention, equilibration sequence utilized in the operation

3
 5 EP 0 434 207 A2 6

of the present invention. a gas such a helium into the pycnometer 10. A first
Fig. 12 is a graphical representation of the drop flow restrictor 26 is placed on the inlet line 25
in pressure in the sample chamber during ex- before it enters the interior of the block 11. The
pansion of gas into the expansion chamber. first flow restrictor 26 is a highly compacted and
Detailed Description of Preferred Embodiment 5 small metal filter or a length of small inner diameter
tubing and its function is to control the inlet gas
Referring now in more detail to the drawing in rate and the rise of gas pressureinthe sample
which like numerals refer to like parts throughout chamber 20.
the several views, Fig. 1 shows a pycnometer 10 Extending from the first valve 17 is a passage-
embodying the invention. Generally described, the 70 way 30 drilled horizontally into the interior of the
pycnometer 10 includes a block 11, with a top block 11. This passageway 30 connects the first
plate 12 affixed to the top of the block. The block valve 17 with the sample chamber 20. A second
11 rests on and is affixed to a bottom plate 13. The passageway 31, also drilled horizontally into the
block 11, top plate 12, and bottom plate 13 are interior of the block 11, extends from the bottom of
made of a material of high thermal conductivity 75 the sample chamber 20 to a pressure transducer
such as aluminum. On the exterior of the pyc- 16 located on the exterior of the block. The pres-
nometer are positioned a cap assembly 15, a pres- sure transducer 16 measures the gas pressure in
sure transducer 16 and valves 17, 18 and 19. the sample chamber 20.
Referring to Figs. 2, 3 and 5, the pycnometer Another passageway 34 joins the sample
10 also includes a sample chamber 20, bored from 20 chamber 20 with the expansion chamber 21. A
above into the interior of the block 11. An expan- second flow restrictor 35 and cut off valve 18 are
sion chamber 21 is also located in the interior of located in this passageway. This second flow re-
the block 11 and is formed by drilling upwardly strictor 35 limits the rate of pressure decrease in
from the bottom surface of the block. The volume the sample chamber 20 thereby avoiding fluidiza-
of the expansion chamber 21 is approximately half 25 tion and carryover of particles from the sample
the volume of the sample chamber. The two cav- chamber 20 into the expansion chamber 21. The
ities are bored in close proximity to each other to valve 18 permits or prevents gas flow between the
ensure maximum temperature uniformity and sta- sample chamber 20 and expansion chamber 21.
bility. Also located in the passageway 34 is a flow limiting
A circular orifice 22 is located in the top plate 30 valve 33, connected in parallel with the restrictor
12, positioned over the opening of the sample 35. During expansion of gas from the sample
chamber 20. This orifice 22 is sized to receive the chamber 20 to the expansion chamber 21, the
cap assembly 15. The cap assembly 15, when difference in pressure between the two chambers
placed through orifice 22 and twisted, seals the tends to create an initial surge in the flow rate of
sample chamber 20 in a manner described below, 35 the expanding gas through the passageway 34, and
thereby insuring a fixed volume in the chamber. this can result in fine powder particles of the sam-
Two rollers 65 are rotatably mounted on shafts 66 ple becoming entrained in the gas stream. The
projecting inwardiy horizontally from opposite sides restrictor 35 maintains the flow rate sufficiently low
of the wall of the orifice 22. As described below, to avoid such entrainment. However, in typical pyc-
the cap assembly 15 engages the rollers 65 when 40 nometer operation, it may require up to 20 minutes
the chamber is being seals for final pressure equilibrium between the cham-
Located on the top surface of the block 11 and bers to be established across the restrictor 35.
surrounding the opening of the sample chamber 20 Therefore, the flow limiting valve 33 is constructed
is a horizontal annular platform 24. The platform 24 to bypass the restrictor 35 when the pressure dif-
is within the circumference of the orifice 22, and 45 ference between the chambers has been reduced
provides a smooth bearing surface for parts of the enough so that the unrestricted flow of gas will not
cap assembly 15. Surrounding the annular platform cause entraiument. The valve 33 is a type of float
24 is an annular groove 25. The circumference of valve in which a ball 39 is lifted by gas pressure
the annular groove 25 is equal to the circumference against a seat 38 consisting of an o-ring seal. In
of the circular orifice 22 and the circumference of a 50 this position, the valve 33 seals off a bypass pas-
ramp 42 (described in detail below) of the cap sageway 32, which connects the sample chamber
assembly 15. The groove 25 matingly receives the to the expansion chamber while bypassing the re-
ramp 42 when the cap assembly 15 is sealing the strictor 35. The ball 39 is preferably made of steel.
sample chamber 20. The precise size and mass of the ball and the size
An inlet line 25 extends from a source of gas 55 of the ball cavity of the valve 33 are selected
(not shown) through the top plate 12 and connects depending on the system volume of the pycno-
to a first valve 17 positioned on the exterior of meter 10, the gas pressure level at which the
block 11. The inlet line 25 allows the introduction of instrument will operate, and the size of the sample

4
 7 EP 0 434 207 A2 3

particles, so that the flow rate out of the sample ramp 42. Removal of material to form inclines b6
chamber will not exceed a selected value beyond and 64 creates an L-shaped cross-section in two
which entrainment is likely. When the gas pressure sections of the ramp 42, with the inclines forming
lifting the ball 39 is insufficient to hold it against the the horizontal leg of the "L" at the bottom of the
seat 38, the ball drops and the gas flowing from the 5 ramp. The vertical leg forms an inner wall 43 of the
sample chamber 20 into the expansion chamber 21 ramp 42.
may flow more freely through the passageway 32, The two inclines 63 and 64 are separated by
which bypasses the restrictor 35. By causing this solid sections 80,81 through which screw openings
bypass to occur after the pressure difference be- 75,76 are formed on the bottom of the ramp 42.
tween the chambers no longer presents a danger w Cutouts 70,71 are formed in the inclines adjacent
of entrainment of fine particles, the time for expan- the solid sections 80,81 .
sion of the gas from the sample chamber to the The cap assembly 15 includes a generally cy-
expansion chamber may be reduced from about 20 lindrical sealing cup 41 positioned within the recess
minutes to about 2 to 3 minutes. Shortening the 46 of the housing 47 and the center of the ramp
time of expansion helps the accuracy of the pyc- 75 42. The sealing cup 41 is preferably formed from
nometer 10 because the device is more likely to aluminum. A circular recess 50 is formed in the top
remain at a constant temperature during the shorter surface of the sealing cup 41. This recess 50 is
analyses time. sized to hold two flat washers 53 and 54 and two
The parameters of the valve 33 based on the belville washers 55 and 56. The sealing cup 41
criteria listed above are preferably selected to re- 20 also includes a recess 51 formed in its bottom
sult in opening of the bypass line 32 when the surface.
pressure within the sample chamber has fallen 75- An annular groove 57 surrounds the opening of
90 percent of its total drop during expansion be- the recess 51 . A lightly greased O-ring 60 is placed
tween the chambers. into the interior of the groove 57.
A fourth passageway 36 is drilled horizontally 25 An inner annular surface 61 is located between
into the block 11 and connects the expansion the opening of the frustoconical recess 51 and the
chamber 21 to an exhaust line 37. A third valve 19 annular groove 57. An outer annular surface 62 is
is located within the passageway 36 and controls located between the groove 57 and the exterior
the venting of gas out of the expansion chamber 21 cylindrical surface of the sealing cup 41 . The outer
into the environment. The exhaust line 37, the 30 annular surface 62 makes metal-to- metal contact
valves 17, 18, 19 and the pressure transducer 16 with the horizontal annular platform 24 surrounding
are all positioned on the rear wall of the pyc- the opening of the sample chamber 20 when the
nometer block 11. chamber is sealed. The inner annular surface 61
The problem of entrainment of fine particles of does not make metal-to-metal contact when the
the sample can also occur when the valve 19 is 35 cap assembly 15 is sealing the sample chamber
opened to begin venting of the system. When the 20, but rather defines a gap which is a part of the
valve 19 is opened, the first surge of gas along the feed volume of the sample chamber.
passageway 34 lifts the ball 39 and seals off the At the upper surface of the sealing cup 41 , an
bypass line 32. Thus, the initial surge prevents annular flange 69 surrounds the cup 41 , extending
entrainment. As in the case of expansion between 40 beyond the vertical wall 43 of the ramp 42, but
the chambers, the bypass 32 is opened when the ending within the walls of the cylindrical recess 46
pressure between the sample chamber and the of the housing 47. Thus, the sealing cup 41 can
restrictor is insufficient to hold the ball 39 against move vertically with respect to the housing 47 and
the seat 38. When this occurs, the gas flow through the ramp 42, through a short distance, but is en-
the less restrictive passageway 32 allows the sys- 45 trapped by the wall 43 and cannot fall out of the
tem to reach atmospheric pressure much more cap assembly 15. Furthermore, the washers 55 and
quickly than it would through the restrictor 35. 56 are sized to urge the cup 41 outwardly from the
The cap assembly 15 is illustrated in Figs. 6 housing 47.
and 7. A knob 40 is found on the top portion of the Assembly of the cap assembly 15 is illustrated
cap assembly 15. A series of projections surround 50 in Fig. 7. Two screws 72,73 are threaded through
the top periphery of the knob 40, enabling the the screw openings 75,76 and attach the ramp 42
operator to securely grip and twist the cap assem- to the housing 47, confining the sealing cup 41 as
bly 15 into its proper sealing position. The knob is described above.
attached to a sealing cup housing 47 which defines After the sample to be analyzed is placed in
a cylindrical recess 46 in its lower surface. 55 the sample chamber 20, the operator places the
Attached to the lower surface of the housing 47 cap assembly 15 into the orifice 22. The operator
is an annular ramp 42, as shown in Figs. 6,7 and 8. must align the cap assembly 15 such that the
Inclines 63 and 64 are defined on either side of the cutouts 70,71 will permit the rollers 65,66 to pass

5
 9 EP 0 434 207 A2 10

through the bottom of the ramp 42, thereby engag- output of the board 21 1 is directed to the CPU 200
ing the inclines 63,64. The cap assembly 15 is now through the backplane 205. A basic analog to digi-
ready to seal the sample chamber 20. tal conversion is performed wherein these pulses
To effect this sealing operation, the operator are integrated over a fixed period of time, arriving
twists the cap assembly 15 in a counter-clockwise 5 at a number that is proportional to tho output of the
direction, moving the inclines 63,64 along the roll- pressure transducer 16.
ers 65, 66 which apply a downward force on the A valve controller board 215 contains all the
cap assembly. The belville washers 55,56 then logic for controlling the valves 17,18 and 19 in
urge the sealing cup 41 onto the platform 24. This response to signals from the CPU. This valve con-
camming action ensures metal-to-metal contact be- 10 trailer board 215 is connected to the CPU 200 and
tween the surface 62 of the sealing cup 41 and the also to the backplane 205.
platform 24, as well as the compression of the CD- Completing the electronics of this system are
ring 60 against the platform 24. The volume of the conventional valve LED's 220, an LCD display 221
sample chamber 20 is now fixed, and the pyc- and a keypad 222, all three plugged directly into
nometer 10 is ready for operation. 75 the backplane 205. The I/O controller board 211
The cap assembly 15 shown in Fig. 6 is rotat- also contains logic for handling user input through
ed counter-clockwise to generate a sealing force, the keypad 222, and output to the set of LED's
and therefore is left-handed. It will be appreciated 220, which display the open or closed status of the
that the cap can also be designed to be right- valves, and the LCD display 221, which displays
handed. 20 run status messages, error messages, and results
Fig. 5 illustrates how the pycnometer 10 is of the analysis. Output to compatible devices
used in conjunction with a conventional micropro- through an RS-232 connector or similar interface
cessor. The microprocessor controls the various (not shown) can also be provided.
elements of the system during operation in a man- The above-described electronic components
ner described below. In a conventional manner, the 25 are conventional. However, automatic operation and
computer operates valves 17,18 and 19 as well as control readily permits the helium to be established
monitoring the pressure measurements taken by about the sample. Computerization of the pycno-
the pressure transducer 16. The computer also meter 10 allows pressure measurements to be car-
accepts the various keypad inputs and provides the ried out rapidly so that external influences such as
appropriate displays, such as LED's and LCD's. 30 ambient temperature and pressure changes have
The central processing unit 200 plugs into a no time to exert significant effects on test results.
backplane 205. The backplane 205 is the main Also rapid repetitive testing allows attainment of a
communication bus interconnecting the entire sys- constant value reading thereby signaling a uniform
tem. A power supply board 206 also plugs into the temperature throughout the pycnometer 10 and
backplane 205 and is a regulated 5V DC for digital 35 insuring accurate test results.
logic. This power supply board 206 supplies power Operation of the pycnometer 10 is described
to everything in the system except for valves 17,18 as follows, with particular reference to the flow
and 19. charts of Figs. 9, 10 and 11 which shows a se-
The valves 17,18 and 19 are powered by a quence of steps taken by the operator and per-
valve power supply 207, which also plugs into the 40 formed by the pycnometer.
backplane 205. The valves take a maximum of 15 Describing the operation of the system in more
instantaneous watts to drive and require a 20V detail, block 1 of Fig. 9 indicates the parameters
pulse, 35 msec in duration, to open or close. It is and instructions the operator must input in order for
important that the valves 17, 18 and 19 do not the system to carry out an analysis. These values
generate excess heat when opening and closing 45 include the number of purges, the purge fill pres-
due to the possibility of changing the temperature sure, the run fill pressure, the maximum number of
of the block 11 and affecting test results. There- run attempts, the acceptable equilibrium rate, and
fore, the valves are operated with a pulse of current the volume tolerance defining an acceptable result.
rather than having a continuous current supply. These values and their significance will be ex-
A voltage to frequency (V to F) converter 210 50 plained in detail below. After these values are input
receives the output of the pressure transducer 16 by the operator, valves 17,18 and 19 are closed.
and is connected to a transducer and input/output Before operating the apparatus to determine
(I/O) controller board 211. The I/O controller board the volume of a sample, the pycnometer 10 must
21 1 is also plugged into the backplane 205. The V be flushed or purged of all unwanted moisture and
to F converter 210 takes the voltage output from 55 other condensable vapors that entered when the
the pressure transducer 16 and converts it to a sample was manually deposited inside the sample
pulse train whose frequency is proportional to the chamber 20.
voltage output from the pressure transducer. The This purging ensures the accurate calculation

6
 1 EP 0 434 207 A2

Df the volume of the sample. The purging infuses After the purging ot tne pycnometer iu ot
the chambers and passageways with helium. The unwanted vapors is complete, the computer will
sample chamber 20 and expansion chamber 21 are then execute a zeroing operation to establish a
pressurized above atmospheric pressure and then base line atmospheric pressure in the pycnometer
axpanded back to atmospheric pressure. This step 5 10. In block 10 of Fig. 9, the expansion valve 18
Df pressurizing above atmosphere and then ex- and vent valve 19 are opened. Equilibrium in the
panding back to atmosphere is repeated for a set system is established in block 11, according to the
number of purges. These series of purges will "equilibrium" routine of Fig. 11. In block 1 of Fig.
desorb and expel the unwanted vapors and gases 11, a high precision pressure reading is selected
from the chamber and passageways. w by the system. The pressure in the sample cham-
Blocks 3-9 of Fig. 9 illustrate the purging ac- ber 20 is measured by the pressure transducer 16
tion performed by the pycnometer to flush the approximately once each second. If the pressure
unwanted gases. The expansion valve 18 is open reading is equal to an overrange pressure, the
and the fill pressure is set to purge fill pressure. In operation is terminated. If the pressure is not over-
blocks, helium is then introduced into the sample 75 range and eight seconds has elapsed, the equilib-
chamber 20 according to the "fill" routine of Fig. rium pressure is calculated by using a conventional
10. In block 2 of Fig. 10, valve 17 is opened and a Savitsky-Golay nine point smoothing routine to fit a
10 millisecond timer is activated. The pressure curve with four prior and four subsequent pressure
transducer 16 measures the pressure inside the readings. A Savitsky-Golay eleven point smoothing
sample chamber 20. The pycnometer 10 is then 20 routine could also be used.
tested to make sure the gas injectors are mechani- The equilibrium rate, or how fast the pressure
cally functioning properly and not overpressurizing is changing within the sample chamber 20, is then
the system. If the gas injectors do not meet the determined. The equilibrium rate is calculated us-
required purge fill pressure within 300 seconds, or ing a conventional nine point differential smoothing
if the system is overfilled, the fill valve 17 will close 25 routine. This curve is fit with four prior and four
and the operation is terminated because of an error subsequent smoothed equilibrium pressures cal-
situation. If the system is not overpressurized, the culated in block 7 of Fig. 11.
pressure is measured in the sample chamber 20 After the equilibrium rate is calculated in block
after a period of 10 milliseconds has elapsed from 8 of Fig. 11, it must be compared to the previously
the time after the fill valve 17 was opened, as 30 set maximum allowable rate of pressure change. If
determined in block 9. This pressure measurement the equilibrium rate is less than or equal to the
is then tested to see if it is at least 99.95% of the maximum, the equilibration subroutine is complet-
purge fill pressure. If it is not within this tolerance, ed. If, however, the equilibrium rate is greater than
the 10 millisecond timer is activated again and the the maximum, the operating sequence in blocks
sequence in blocks 3-10 is repeated until the 35 7-9 is repeated until the system is equilibrated, or
pressure measurement is within the predetermined a maximum time period has expired, as tested in
tolerance of 99.95% of the purge fill pressure. block 12. If the system cannot equilibrate within the
Once the pressure measurement is within this maximum time allowed, an error message is pro-
predetermined tolerance, the fill valve 17 is closed. duced in block 13 and operation is terminated.
The instrument waits two seconds and checks the 40 Returning to block 12 of Fig. 9, the vent valve
pressure. If it is below the required tolerance, the 17 is closed and the equilibrium subroutine illus-
fill valve 17 is briefly opened and then shut. The trated in Fig. 11 and described hereinabove is
instrument repeats this series of steps until the repeated. After the second equilibration sequence,
pressure has stabilized to at least 99.95%of the fill a new zero offset pressure is calculated. This pres-
pressure. The program returns to block 6 of Fig. 9, 45 sure establishes a baseline atmospheric pressure
and the vent valve 19 opens, allowing the unwanted in the system before tests on samples are run. The
gases to be flushed out of the system. The se- expansion valve 18 is closed and the system is
quence for purging the system in blocks 3-8 of now ready to analyze the unknown sample pre-
Fig. 9 is repeated until the set number of purges, viously deposited into the sample chamber 20.
inputted by the operator, is reached in block 9. In 50 Blocks 16-39, Fig. 9, refer to the run routine
the preferred embodiment, the number of purges executed by the computer. In block 16 of Fig. 9,
needed to adequately flush the pycnometer 10 of the fill pressure is set to the run fill pressure. The
moisture and other condensable vapors is variable sequence for filling the system in Fig. 10 is then
from three for dry, nonporous samples up to 99 repeated to fill the sample chamber 20 to the run
which might be required for moist, porous samples 55 fill pressure. After the filling subroutine is complete,
of high affirmity for water vapor or other gases. the computer then executes the equilibration sub-
More frequently, the usual sample will require five routine illustrated in Fig. 11. After the system is
to ten purges. equilibrated, the expansion valve 18 is opened and

7
 13 EP 0 434 207 A2 14

the helium expands into the expansion chamber sion valve 18 is closed after equilibrium The
21. During the initial expansion of the gas, the zeroing and run sequences in blocks 10-21 of Fig.
pressure within the sample chamber 20 and the 9, are repeated until five runs have been completed
passageway 34 closes the flow limiting valve 33. as tested in block 22. When five runs have been
The gas flows through the restrictor 35 until the 5 completed according to the preprogrammed sched-
pressure in the passageway 34 is no longer high ule, a sequence of tests are performed comparing
enough to close the valve 33. During the remainder the five runs, to make evident the presence or
of the expansion of the gas, the gas can flow more absence of a progression of results to a constant
freely through the bypass passageway 32, resulting value. The constant value happens to be the sam-
in a much shorter time to reach equilibrium. 10 pie volume. Its attainment signals that uncon-
Fig. 12 shows a graphical representation of the taminated helium has been established and any
drop in pressure in the system during expansion temperature discrepancy between the sample and
from the sample chamber to the expansion cham- the system has been dissipated.
ber. The sample chamber is filled with gas to a Blocks 25- 30 of Fig. 9 illustrate the above-
starting pressure Ps, which may for example be 75 described sequence of tests. These sequence of
19.5 psig. The solid line initially represents the tests are in essence a volume check test to deter-
drop in pressure which occurs through the restric- mine if the volume deviation between the five suc-
tor 35. As the pressure within the sample chamber cessive runs is within the previously set volume
drops, the rate at which gas flows through the tolerance. After five runs are completed, the vol-
restrictor, and therefore the rate at which the pres- 20 ume of the first run is subtracted from the volume
sure falls slows dramatically. In this example, the of the fifth, or last run. The absolute value of this
chambers will equilibrate at the pressure Pe, of number is termed the volume deviation. If the vol-
12.5 psig. The dashed line A shows how the rate of ume deviation is less than the allowable volume
pressure decrease toward Pe would slow more and tolerance, the sequence in blocks 25-30 is re-
more as the equilibrium pressure was approached. 25 peated calculating the volume deviation between
According to the invention, the valve 33 is selected the fifth or most recent run and the second, third
so that the ball 39 drops at the point on the curve and fourth run, respectively, in that order.
indicated by Pv. This results in a much more rapid If the volume deviation between the fifth and
drop of the actual pressure to the equilibrium pres- four previous runs is within the predetermined vol-
sure Pe, as shown by the solid line in the drawing. 30 ume tolerance, the system concludes that the con-
When the vent valve 19 is subsequently opened, a stant value referred to above is reached and a
curve having a similar shape would be generated, Boolean variable representing adequate precision
although the flow limiting valve 33 will open propor- is taken to be true. At this point, valves 17, 18 and
tionally slightly earlier than during the expansion 19 are closed, in block 31 of Fig. 9. The expansion
step. It should be noted that the rate of pressure 35 valve 18 is then opened; after five seconds the vent
decrease after the valve 33 opens at Pv is no more valve 19 is opened and the system is allowed to
than the initial rate when the valve 18 is first equilibrate to atmospheric pressure. After the
opened. Fig. 12 represents a curve shape obtained equilibration is complete, the expansion valve 18
for a helium pycnometer of about 100 cubic centi- and vent valve 19 are closed. Volume and density
meters sample capacity operating between ap- 40 are calculated in block 37, output reports are print-
proximately 20 psig and atmospheric pressure. ed and operation is terminated.
Those skilled in the art will understand that a If, however, the volume deviation as tested in
flow limiting valve paired with a restrictor as shown block 27 is greater than the volume tolerance dur-
could also be used to modify the rate of evacuation ing any one of the sequence tests in blocks 25-30
of gas from around a fine powder from atmospheric 45 of Fig. 9, the precision is set as not correct in block
pressure to vacuum conditions, or could be used to 28 and the pycnometer will repeat the zeroing and
regulate the readmission of gas to a previously run operations described in blocks 10-22. After
evacuated powder. In both cases entrainment of this additional run, the computer will determine the
particles can be a problem, and the invention volume deviation between the most recent run and
would provide for the valve to seal off initially so the four runs preceding it. Only if the volume
allowing a limited restricted gas flow, and then to deviation is less than the volume tolerance in five
open allowing final equilibrium conditions to be successive runs, will a constant value be accepted.
attained at a much more rapid rate. If this constant value is not attained after a maxi-
When the system reaches Pe, the system is mum set number of runs, tested in block 23, the
then equilibrated, since to insure optimum test re- 55 operation is terminated.
sults, equilibrium pressures must be carefully es- The detailed description of the operation of the
tablished both before and after each expansion. pycnometer in conjunction with a computer has
Referring now to block 21 of Fig. 9, the expan- been described hereinabove and illustrated in the

8
 15 EP 0 434 207 A2 16

flow charts of Figs. 9, 10 and 11. The following now determine

discussion merely describes the theory behind de- The same above described steps are per-
termining the volume of a sample placed inside the formed by the system to determine the volume of
pycnometer, used in performing the calculations of the unknown sample. First, this sample is placed in
block 37 of Fig. 9. The discussion does not reflect 5 the sample chamber 20 and the operator properly
the entirety of operations performed by the com- pushes and twists the cap assembly 15 into the
puter when ascertaining the volume of the sample. block 11. The sample chamber 20 should be seal-
The pycnometer 10 is of the comparison de- ed and its volume fixed. As performed during the
sign. Therefore, it first must be calibrated. Two calibration stage and described in detail above,
tests must be performed since the two volumes of 10 helium is introduced into the pycnometer 10, and
the sample chamber 20 and the expansion cham- the pressure transducer 16 reads the Pi* pressure.
ber 21 must he established. The first test is run The gas is then expanded into the expansion
pursuant to the flow charts described above without chamber 21 and P2* is read by the pressure trans-
any sample in the sample chamber 20. Both cham- ducer 16. The following equation is obtained:
bers should contain gas at ambient pressure or 15 Pi * (Vc-Vj) = P2* (Vc-Vy + VE) (5)
zero gauge pressure and valves 17, 18 and 19 Solving for the volume of the sample Vu gives
should be closed. Valve 17 is opened and the Vu = Vc-[VE/(1-Pi/P2)] (6) Hence, using equation
sample chamber 20 is charged to P1 gauge pres- 6, the volume of the unknown can be ascertained
sure by introducing helium into the sample cham- because Vc and VE were determined from equa-
ber by way of the inlet line 25 and passageway 30. 20 tions 3 and 4 respectively and Pi* and P2* were
Pressure transducer 16 reads Pi. recorded by the pressure transducer.
The computer then closes valve 17 and opens It should be understood that the foregoing re-
valve 18. The helium then travels through passage- lates only to a preferred embodiment of the
way 34 expanding into the expansion chamber 21 , present invention, and that numerous changes and
thus reducing the pressure in the sample chamber 25 modifications therein may be made without depart-
20 to P2. This pressure is read and recorded by ing from the spirit and scope of the invention as
the pressure transducer 16. Valve 19 is opened, defined in the following claims.
allowing the helium to exit the pycnometer 10 by
way of passageway 36. The following relationship Claims
is obtained: 30
P1Vc = P2(Vc + VE). (1) 1. An apparatus for determining the volume of a
where Pi = Pi gauge pressure in sealed sample solid substance including a sample chamber (20)
chamber; containing said substance, an expansion chamber
Vc = volume of sample chamber; (21) connected by a passageway (34) to said sam-
P2 = P2 gauge pressure taken after expansion into 35 pie chamber, gas supply means for introducing a
expansion chamber; and gas under pressure into one of said sample cham-
VE = volume of expansion chamber. ber (20) and said expansion chamber, expansion
Next, an object of known volume VK is placed valve means (1 8) for permitting flow of gas through
in the sample chamber 20 and the operator repeats said passageway, vent means (19) for venting one
the above steps of introducing the helium into the 40 of said chambers to atmosphere, and means (16)
sample chamber and allowing it to expand into the for measuring the pressure of gas within one of
expansion chamber. The following relationship is said chambers, characterized by:
obtained: control means (200-215) for:
Pi*(Vc-Vk) = P2*(Vc-Vk + Ve). (2) (a) operating said gas supply means to pressur-
Where: VK = volume of known sample; 45 ize with a gas the one of said chambers contain-
Vc = volume of sample chamber; ing said pressure measuring means (16);
VE = volume of expansion; Pr = before expan- (b) operating said pressure measuring means to
sion pressure with known volume; and measure the pressure in said one chamber;
P2* = after expansion pressure with known volume. (c) operating said expansion valve means (18) to
Solving equation (1) for VE gives: 50 allow expansion of said gas through said pas-
VE = Vc[(Pi-P2)/P2] (3) sageway (34) into said other chamber;
Equation 3 establishes the relationship between VE (d) operating said pressure measuring means to
and Vc. Incorporating equation 3 into equation 2 measure the pressure in said connected cham-
and solving for Vc yields the following equation: bers;
Vc = VK(Pi *-P2*)/[(Pi *-P2*)-(Pi -P2)(P27P2)] (4) 55 (e) calculating a first volume of said sample;
Equations (3) and (4) establish the respective (f) storing said first volume;
volumes of the sample chamber and expansion (g) operating said vent means (19) to vent said
chamber. The volume of the unknown sample is chambers to atmosphere;

9
 17 EP 0 434 207 A2 18

(h) repeating (a) through (d); tion; and

(i) calculating an additional volume of said sam- means (63,65) for selectively retaining said cap in
ple; said sealing position.
0) comparing two or more of said volumes; 8. The apparatus of Claim 7, wherein said cap (15)
(k) responsive to said compared volumes being 5 is characterized by:
within a predetermined tolerance, accepting one a body (47);
of said compared volumes as the volume of said a plunger (41) mounted for movement with respect
sample; and to said body, said plunger defining said rigid por-
(I) responsive to said compared volumes being tion (62) and carrying said gasket member (60);
outside said predetermined tolerance, repeating 10 and
(h)-(j) until said compared volumes are within means for urging said plunger away from said
said predetermined tolerance. body such that when said cap is in said sealing
2. The apparatus of Claim 1, wherein said gas position, said plunger engages said continuous sur-
supply means is further characterized by: face (24) and and said gasket is compressed.
supply valve means (17) for admitting gas from 75 9. The apparatus of Claim 8, wherein said rigid
said gas supply into said one chamber; and portion defined by said plunger (41) is character-
fill control means (215) for operating said supply ized by an annular projection shaped to be matin-
valve so as to admit gas into said one chamber to gly received by said continuous surface (24); and
establish a predetermined fill pressure in said one said gasket member (60) is characterized by an o-
chamber within a predetermined tolerance of said 20 ring received in a groove (57) defined in said
predetermined fill pressure. annular projection.
3. The apparatus of Claim 2, wherein said fill con- 10. The apparatus of Claim 8, wherein said means
trol means is characterized by: for selectively retaining said cap (15) in said seal-
means (200,211,221) for generating an error signal ing position engages said body (47) while permit-
if the pressure in said one chamber exceeds said 25 ting movement of said plunger (41); and wherein
fill pressure by more than said tolerance; and said means for urging said plunger comprises a
means (200, 215) for momentarily opening said spring (55, 56) interposed between said body and
supply valve (17) if the pressure in said one cham- said plunger.
ber is lower than said fill pressure by more than 11. The apparatus of any of Claims 8 to 10,
said tolerance. 30 wherein said plunger (41) is slidably mounted for
4. The apparatus of Claim 2 or 3, wherein said movement within a cavity (46) defined in said body.
supply valve (17), said vent valve means (19) and 12. The apparatus of any of Claims 1 to 11,
said expansion valve means (18) each comprises a wherein said apparatus is further characterized by
pulse operated valve. selective restrictor means (33,35) for permitting
5. The apparatus of Claim 4 wherein said cham- 35 flow of gas through said passageway (34), char-
bers, said valves, and said pressure measuring acterized by:
means are contained within a single block (11) of a first position in which flow of said gas is re-
material of high thermal conductivity. stricted to remain at or below a predetermined rate;
6. The apparatus of Claim 5, further characterized and
by: 40 a second position in which flow of said gas through
first restrictor means (26) for limiting the flow rate said passageway is less restricted;
of gas between said gas supply means and said said restrictor means switching from said first posi-
one chamber; and tion to said second position responsive to the pres-
second restrictor means (35) for limiting the flow sure in said one chamber dropping below a pre-
rate of gas between said chambers. 45 determined pressure during expansion of said gas
7. The apparatus of any of Claims 1 to 6 further through said passageway into said other chamber.
characterized by a removable closure (15) for said 13. The apparatus of Claim 12, wherein said re-
sample chamber (20), comprising: strictor means is characterized by:
a continuous surface (24) surrounding an opening a restricted line (35) connecting said chambers;
defined by said sample chamber; 50 and
a cap (15) including a rigid portion (62) engaging a float valve (33) connected to bypass said re-
said sample chamber to define said fixed volume stricted line, including a float member (39) sup-
when said cap is in a sealing position with respect ported in said first position against a seat (38) by
to said opening; the pressure of gas in said one chamber until said
a compressible gasket member (60) mounted in 55 pressure falls below said predetermined pressure.
said cap such that said gasket member is com- 14. A method for determining the volume of a solid
pressed in sealing relationship against said continu- substance contained in a sample chamber (20) of a
ous surface when said cap is in said sealing posi- pycnometer having an expansion chamber (21) and

10
 9 :P 0 434 207 A2 !U

a passageway (34) connecting said chambers in- terminating admission ot said gas wnen tne pres-
cluding the steps of (a) pressurizing one of said sure in said chamber is within a predetermined
chambers with a gas, (b) measuring the pressure in tolerance of said predetermined fill pressure com-
said pressurized chamber, (c) allowing expansion onses the steps of:
of said gas into said other chamber, (d) measuring 5 (a) terminating admission of said gas;
the pressure in said connected chambers, and (e) (b) measuring the pressure in said chamber;
calculating a first volume of said sample, character- (c) generating an error signal if the pressure in
ized by the steps of: said chamber exceeds said fill pressure by
(f) storing said first volume; more than said tolerance;
(g) venting said chambers to atmosphere; w (d) momentarily admitting additional gas if the
(h) repeating steps (a) through (d); pressure in said chamber is lower than said fill
(i) calculating an additional volume of said sam- pressure by more than said tolerance; and
ple; (e) repeating steps (b) through (d) until the pres-
i) comparing two or more of said volumes; sure in said chamber is within said tolerance.
(k) accepting one of said compared volumes as 75 19. The method of any of Claims 14 to 18 wherein
the volume of said sample if said compared said step of allowing expansion of said gas into
volumes are within a predetermined tolerance; said other chamber is characterized by:
and limiting the flow rate of said gas through said
(I) repeating steps (h) through (j) if said com- passageway (34) during the initial transfer of gas to
pared volumes are outside said predetermined 20 said other chamber; and
tolerance until said compared volumes are with- responsive to the pressure in said one chamber
in said tolerance. dropping below a predetermined pressure, permit-
15. The method of Claim 14 further characterized ting increased flow of gas through said passage-
by purging unwanted gases from said chambers way.
(20,21), characterized by the steps of: 25 20. The method of Claim 19, wherein said step of
(m) pressurizing said connected chambers with limiting the flow rate of said gas is characterized by
a gas to a pressure above atmospheric pres- forcing said gas to pass through a restricted line
sure, by opening an inlet valve (17) to introduce (35), and wherein said step of permitting increased
a gas into said chambers from a pressurized flow is characterized by bypassing said restricted
source of said gas, 30 line.
(n) closing said inlet valve after pressurization of
said chambers,
(0) waiting for a predetermined period of time;
(p) opening an outlet valve (19) to allow said gas
to expand to atmosphere; and 35
(q) repeating steps (m) through (p).
16. The method of Claim 15, wherein said chamers
consist of a sample chamber (20) and in expansion
chamber (21), and wherein said step of pressuriz-
ing said chambers is characterized by closing an 40
internal flow valve (18) between said chambers;
opening an inlet valve (17) to introduce a gas into
said expansion chamber from a pressurized source
of said gas; closing said inlet valve after pres-
surization of said expansion chamber; opening said 45
internal flow control valve such that said gas ex-
pands into said sample chamber (20) at a pressure
above atmospheric pressure; waiting for a predeter-
mined period of time; and opening an outlet valve
(1 9) to allow said gas to expand to atmosphere. 50
17. The method of any of Claims 14 to 16, wherein
said step of pressurizing one of said chambers with
a gas is further characterized by the steps of:
admitting a gas into said chamber; and
terminating admission of said gas when the pres- 55
sure in said chamber is within a predetermined
tolerance of a predetermined fill pressure.
18. The method of Claim 17, wherein said step of

11
EP 0 434 207 A2

12
EP 0 434 207 A2

3
EP 0 434 207 A2

14
-1
1
EP 0 434 207 A2
EP 0 434 207 A2

17
 r u 'tot t u t

:nter u s e r V.
NPUT VALUES VENT VALVES |

;lose a l l 7. EQUILIBRATE ]
VALVES

OPEN CLOSE
Z. VENT VALVE
EXPANSION VALVE

SET FILL P R E S S U R E
EQUILIBRATE
>URGE FILL PRESSURE

CALCULATE NEW
rILL 14. ZERO OFFSET PRESSURE

OPEN CLOSE
10. EXPANSION VALVE
VENT VALVE

SET FILL P R E S S U R E
WAIT 5 lb.
7. SECONDS RUN FILL PRESSURE

CLOSE EXPANSION FILL

3. if.
VENT VALVES
1

9.
 ROM rlu 9cu

8. EQUILIBRATE |
SLETED RUNS
SET I = 4
25. SET PREC - OK

OPEN
19.
EXPANSION VALVE
>t I VULUMfc UtV =
CVOL OF RUN X -
VOL OF RUNCX-DI
20. EQUILIBRATE

CLOSE
21.
EXPANSION VALVE

TO C ^ . 1 O
 -> u 434 ZU/ Ai£

HUM 9b

E5

CLOSE A L L
?7. VALVES

OPEN
32.
EXPANSION VALVE

WAIT 5
33.
SECONDS

OPEN
34.
VENT VALVE

35. EQUILIBRATE

CLOSE EXPANSION J
36. VENT V A L V E S

CALCULATE
37. VOLUME A N D
DENSITY

PRINT
38. REPORTS

C ->
TERMINATE
39. OPERATION

9 C
 [ s t a r t }

OPEN
FILL VALVE

START
10 u SEC TIMER

MEASURE
PRESSURE
1

r ILL VALVE

n.

CLOSE
FILL VALVE
FILL VALVE
lyj.

ERROR
MESSAGE

f.

TERMINATE
OPERATION
8.

# A « 7 7 U
_
Z 7 ^
 ' U tJI All l\c.

ELECT HIGH
RECISION
RESSURE
EADING tl CUUluiomuivi n n i c
9 POINT DIFFERENT -
^L SMOOTHED
RESSURE

2 / \

ERROR
MESSAGE

(end)

TERMINATE
OPERATION

n.

WAIT 1 SECOND

SET EQUILIBRIUM
PRESSURE = 9 POINT MESSAGE
S A V - G O L SMOOTHED
PRESSURE 7J .

I c n i v i m « 11
OPERATION