NBSIR 76-1116

STABLE PRESSURE TRANSDUCER

Jack H. Colwell

Institute for Basic Standards

National Bureau of Standards

Department of Commerce

Washington, D. C. 20234

July 1976

Final Report

Prepared for

Aerospace Guidance and Metrology Center

Newark Air Force Station

Newark, Ohio 43055

CCG/Army/Navy

US Army Missile Command

US Army Metrology and Calibration Center

Redstone Arsenal, AL 35809

Naval Plant Representative

Metrology Engineering Center

1675 W. Mission Boulevard

Pomona, California 91766

ABSTRACT

This report describes the work done on the development of a soliddielectric capacitive pressure transducer that is to have the accuracy and long

term stability of which a piston gauge is capable. The temperature and pressure

dependences of nearly one hundred samples have been measured in the process of

trying to find materials for capacitors that v/ould be capable of giving the

requisite pressure resolution but not require excessively elaborate thermostating

.

To minimize temperature effects a technique has been developed whereby the ratio

of two capacitors, made from different materials, is determined. By the proper

choice of materials the temperature dependence of the ratio can be made small

while the pressure dependence remains large. Two pairs of samples have been

found which come close to meeting our requirements, the parallel and perpendicular

cuts of calcite and a Bi 12 Ge 0 2 o (BGO) - As 2 S 3 combination. The latter combination

has the best potential for use in the transducer but samples' of BGO have not been

found which form stable capacitors. The system uses an Invar sample holder in a

commercial pressure vessel and is designed so that it minimizes adiabatic heating

effects and thereby shortens thermal equilibration times and simplifies thermostating.

A limited-range automatic capacitance bridge has been built for use with the

pressure transducer.

Key Words: Adiabatic Heating; Automatic Bridge; As 2 S 3 ; Bi 12 Ge02 o; CaC0 3 ;

CaF 2 ; Capacitance measurement; Evaporated electrodes; Pressure

Transducer

INTRODUCTION

Piston gauges have long been used for high precision pressure determinations and as transfer standards in the dissemination of pressure scales.

These gauges are not simple to use, however, and should more properly be

considered as devices for generating known pressures rather than as devices

•for measuring pressures. The cross-float procedure required to compare

two piston gauges is very tedious. At high pressures, the use of piston

gauges becomes awkward because of the large weights involved and because

of the critical requirements placed on the selection of pressurizing fluids.

In addition, quality piston gauges are expensive.

It would be very advantageous for precision pressure measurements if

a direct-reading pressure transducer could be found which would possess

the accuracy and long-term stability of the piston gauge. We set out to

find a device meeting these requirements and, in addition, to seek one

having the capability of digital readout and possibly automatic balancing.

After a critical review of both existing and proposed pressure measuring

devices we decided to try to develop a capacitive transducer in which the

change in capacitance under hydrostatic pressure of a solid dielectric

capacitor would be measured. The advantage of the dielectric capacitor over

other devices is that using a hard, preferably crystalline, dielectric

material with electrodes deposited directly on its surface, one would expect

no permanent deformation to occur under repeated cycling with hydrostatic

pressure and, therefore, to achieve the required long-term stability.

At the time this work was being initiated, Andeen, Fontanella, and

Schuele (Rev. Sci. Instr. 42, 495 (1971)) of Case-Western Reserve University

were demonstrating the feasibility of such a gauge using single crystals of
*
CaF£ as a dielectric medium. With a CaF£ capacitor, the capacitance changes

only 0.26% when pressurized to 70 MPa (10,000 psi) so that the capacitance

must be measured to 2.6:10 7 in order to determine pressures to a precision

of lrlO 4 at 70 MPa. Using the three terminal capacitor method, modern A.C.

bridge techniques, and accurate ratio transformers, capacitance measurements

can be measured with accuracies of 1:10 7 and with resolution of 1:10 8

.

Piston gauges at 70 MPa have accuracies of about 1:10 5 which is within the

range of accuracy achievable with a CaY

2

capacitor. Tests have not indicated

any instabilities in the capacitors so a gauge using a CaF2 crystal does

approach the basic pressure requirements. The capacitance of the CaF 2

gauge is, however, strongly temperature dependent; 1 mK changes the capacitance 2.6:10 7

, i.e., 1 mK would change a pressure determination at 70 MPa

by 1:10\ Therefore, use of this gauge at the 1:10 5 level would require that

its temperature be maintained to much better than 1 mK. Thermostating to

this level is clearly impractical, especially when one considers the heat

generated in the pressure vessel whenever the pressure is changed and the

long time required to reestablish thermal equilibrium.

As a result, a search was begun for materials which would have a greatly

improved ratio of their pressure to temperature coefficients. Pyrolytic BN

and AS2S3 were found to be more than a factor of ten better than CaF2 but

this does not sufficiently alleviate the thermostating problem. As an

expedient toward getting a working device, we began looking at other ways of

overcoming the temperature dependence of the capacitance measurement. The

bridge method required for the capacitance measurement offered ways of

accomplishing this. One technique was to put capacitors of the same material

in the opposite arms of the Wheatsone bridge circuit so that their capacitances

are in opposition to each other. If one capacitor is pressurized and the
-
other kept at ambient pressure while keeping the- two capacitors in thermal

contact, the temperature will be cancelled to first order. James Miller

of the U.S. Army Missile Command, Redstone Arsenal, has been pursuing

developments along this line. The principal difficulty with this approach

is that it requires the establishment of good thermal contact between a

sample inside the pressure vessel and one outside. In our laboratory,

we decided to concentrate on a variation of this same idea: placing in

opposite arms of the bridge, two capacitors which have nearly equal

temperature dependences but widely differing pressure dependences and

placing both capacitors inside the pressure vessel. In this way, the

temperature dependence of the combination could be largely cancelled out

while retaining a reasonable pressure dependence but, with the two

capacitors in close proximity to each other, thermal equilibration problems

are eliminated. In pursuing this course, we have found only two combinations of materials which meet our requirements as far as temperature

and pressure dependences are concerned, but both combinations turn out

to be less than ideal as transducer materials for other reasons.

We are proceeding with the construction of a transducer based on this

idea in the hope that these materials can be satisfactorily utilized or

that other suitable combinations of materials may be found.
-

-
4

CAPACITANCE MEASUREMENTS

Capacitance Bridge . A schematic of the capacitance bridge used for these

measurements is shown in Fig. 1. The main transformer was hand wound on

a supermall oy toroid. The primary is shielded from the secondaries with a

separate electrostatic shield and a heavy mu-metal shield. The main secondary

is center tapped with a 10:1 turns ratio, the low impedance winding having a

resistance of about 20 milliohms. A second set of center tapped secondaries

with a 1:1 turns ratio is used with the quadrature balance circuit. The

bridge is powered by a General Radio 1311 -A audio oscillator operating at

u>=10 4 (1592 Hz).

The standard capacitors are 100 and 1000 pF General Radio type 1404

capacitors. By placing the appropriate capacitor on the appropriate side of

the 10:1 transformer a full range of 10, 100, 1000, or 10,000 pF can be

obtained. The standard capacitors are maintained in temperature controlled

enclosure that is regulated to a few millikelvins.

The ratio transformers are a Gertsch model 1011 for the capacitance balance

and a Gertsch RT 60 for the quadrature balance. The "phase splitter" circuit

use for the quadrature phase shifter provides several different ranges of

quadrature balance. Two resistors with nominal values of 10 5 and 10 6 ohms have

been specially tuned to be pure resistances at w=104. With one of these resistors

in the bridge circuit the phase shifter can be aligned by nulling the capacitive

component.

The bridge null detector is a Princeton Applied Research model 120 lock-in

detector with a model 112 preamplifier. The bridge imbalance is monitored with

a chart recorder. At a bridge voltage of 70 v.p.p. the bridge resolution is

0.01 ppm.

s'

5

Sample Preparation . The deposition of metallic electrodes on the dielectric

samples has been the most difficult and time consuming problem throughout this

work, both from the standpoint of forming the insulating gaps for the guard

electrodes and because of poor adherence of the electrodes to the samples.

To properly utilize the three-terminal capacitance technique in a parallelplate configuration, the low-voltage electrode should be considerably smaller

than the high-voltage electrode (the difference in the radii of the electrodes

should be at least three times the thickness of the sample). Also, the gap

between the low-voltage electrode and the concentric guard ring should be kept

very small. These restrictions are to minimize the fringing fields so that

materials outside the dielectric sample will have little influence on the

capacitance measurement.

The usual electrode configuration used for three-terminal capacitors is to

have the high-voltage electrode cover one side of the sample, the low-voltage

electrode and its surrounding guard ring cover the other side, and the edge of

the sample left uncoated. We have modified the configuration as shown in Fig. 2,

where the guard ring is coated around the edge of the sample with a separate gap

left between it and the high-voltage electrode. This arrangement assures that

the high-voltage electrode cannot electrically short to the side walls of the

sample holders.

The metal electrodes are applied by vapor deposition and the gaps formed

by masking. The masking rings were ground from hardened steel (both Hampden and

Stentor 02 have been used) and the sharp edges were then lapped flat using a fine

alumina compound. The dimensions of the two rings which are used with 25mm

diameter samples is shown in fig. 2. The attraction between the steel rings

and a small bar magnet is sufficient so that the samples and rings can be supported

in the evaporator in the manner shown in Fig. 2. To eliminate shadowing by the
'
6

ring it is necessary to rotate the sample during the deposition process

and to position the evaporation source at about a 45° angle to the plane of

the sample. With this masking technique we have successfully obtained gaps

around the low-voltage electrode as small as 6ym but to avoid failures we

usually used rings which left gaps of about 15ym. There is no need for the

gap around the high-voltage electrode to be narrow so a much wider masking

ring was used here. With smaller diameter samples, rings of 12.7mm and 8.9mm

diameters have been used and with the smaller diameter rings proportional ly

smaller gap widths have been obtained. Because the samples are coated at a 45°

angle to the source, it is necessary for the sample surfaces to be reasonably

Well polished and flat ("two waves" is adequate) to avoid’ gap failure. It has

been possible on several occasions , however , to vaporize small bridges across

gaps by applying a few tens of volts between the electrode and the guard ring.

We have been using aluminum coatings on nearly all our samples and in

most cases getting good adherence. By good adherence we mean coatings which

cannot be pulled off with Scotch tape. This was accomplished after considerable

trial and error and achieved mainly by getting the samples extremely clean. The

procedure used is to wash the samples with soap and water, rinse thoroughly

with distilled water, alcohol, and Freon, and then ion bombarded in the

evaporator in a glow discharge of air for upwards to one hour prior to coating.

The use of 99.999% aluminum wire also improved the coatings considerably over the

coatings from lower purity wire.

There are still several materials on which we cannot get good adherence

with aluminum. In most cases we can still get good capacitance data with long

term stability so it may be that the Scotch tape test is too stringent.

Sample Holder . The sample holder used for the capacitance measurements is

shown in schematic cross section in Fig. 3. It was designed to provide

flexibility so that, with minor modification, samples of different diameter

or thickness could be run. The center piece has a shoulder on which the

guard ring of the sample rests. The two end pieces are of identical construction and hold the electrical contacts. The electrical contacts are

small gold-plated nickel-deposited bellows, which are 3mm in diamter, 5mm

long and can be compressed up to 1.8mm. The advantage in using the bellows

is that their spring constants are very consistent (90g/mm) so that the force

on the contacts can be predetermined by adjusting the amount that the bellows

will be compressed when the sample holder is assembled. This adjustment is

made by varying the thickness of the Teflon washers which insulate the contacts from the body of the sample holder. The bellows of the high-voltage

contact is usually compressed 1mm (90g load) and that of the low voltage

contact 0.5mm (45g load). In this way, there is sufficient load (45g) on

the sample to ensure that good electrical contact between the guard ring of

the sample and the grounded case of sample holder is maintained. With this

arrangement, we have had no trouble with contacts opening during pressure

cycling.

Five sample holders can be mounted on screw rods extending from the

bottom of the pressure vessel closure as shown in Fig. 4. The high-voltage

contacts are connected by miniature coaxial cables to a connector plate on

the bottom side of the closure. The electrical feed-throughs are connected

to the contacts on the reverse side of this plate. The low voltage contacts

from the five cells are interconnected and brought out of the vessel by a

single lead which is carefully shielded from the others.

Pressure System . The pressure vessel used for this work has an internal

diameter of 3.8 cm (1.5 in.), has an internal length of 25cm (10 in.), and

is rated for 138 MPa (20,000 psi). The vessel has an opening in the bottom

which was used for the pressure connection. The closure was modified with

four openings to accept three shielded twin-ax and one coax feedthrough

(P.L.M. Heydemann, Rev. Sci. Instr. 38-550 (1967)). Subsequently, one of

the twin-ax feedthroughs was replaced by a pressure connection, so that the

pressurizing oil could be forced in from the bottom of the vessel and out

through the top thereby purging the air from the system. This arrangement

permitted the use of only four samples at a time but it had been suspected

that air bubbles were causing some irresproducibility in the zero pressure

capacitance reading.

Pressures are generated by an air operated pump which compresses oil

from a reservoir into a large pressure vessel which serves as a buffer to

smooth out pump strokes. The buffer vessel is valved directly to the research pressure vessel. Pressures are measured with a 276 MPa Heise Bourdon

tube gauge which is connected directly to the pressure vessel. This gauge

is accurate enough (0.3% of full scale) for determining pressure coefficients

but for more accurate pressure measurements a Ruska type 2415, 0-138 MPa

piston gauge has been used.

The pressure system was initially filled with instrument oil but this

had to be removed when it became contaminated with moisture. The system

was subsequently filled with paraffin oil which was found to have a much

higher resistivity than other oils even after long exposure to the atmosphere,

p Z 5 x lO 11 ^.

Thermostat and Temperature Measurement . To thermostat the pressure vessel

it was immersed in a large, insulated, water-glycol bath. Fluid from a

liquid thermostat is pumped into the bath at the bottom and led back- to the

thermostat from the top. A refrigerator circulates methanol at -20°C through

the cooling coils of the thermostat. A heater, controlled by a contact

thermometer, maintains a set temperature in the thermostat fluid. The

temperature of the pressure vessel is measured with a platinum resistance

thermometer. The thermometer is in a brass block which is in good thermal

contact with the pressure vessel. The temperature of the pressure vessel

can be regulated at any point between 0 and 50°C to within 5mK for a period

of hours and within 20 mK for several weeks. The resistance of the platinum

thermometer is measured with Leeds and Northrup, 8069-B Mueller Temperature

Bridge which is operated at 27Hz rather than at DC as intended. By using

AC, the bridge imbalance could be determined with a phase-sensitive detector

and recorded on a chart recorder. Using AC, there is no need for lead

reversals to eliminate "thermals." We ran many comparisons between AC and

DC measurements and, within the bridge resolution (iO. lm.K) ,c ic&hlidiiMrKL no

differences. Presumably, 27 Hz is a low enough frequency that inductive

effects in the Mueller bridge are negligible.
'
CAPACITANCE DATA

We have looked at over one hundred samples during the progress of

this work. In Table 1 , we bring together the temperature and pressure

dependences of the capacitance for most of the different materials studied.

Much of these data are plotted in Fig. 6 together with data by other

investigators on several other materials. The lines joining the values for

the two orientations of anisotropic materials indicated all the values that

could be obtained with samples of intermediate orientations. As can be seen

in Fig. 6, most materials fall into the quadrant of positive temperature

coefficients and negative pressure coefficients. This is as one might

* intuitively expect for the pressure dependence, i.e., the material is less

polarizable at smaller volumes, but the temperature dependence is not

easily explained. There are a reasonably large group of materials (not

shown) with both coefficients negative. These are the paraelectrics of which

the thallous halides are examples. For these, both the temperature and

pressure dependences follow a Curie-Weiss type relation and are usually

rather large. The unifying characteristic of all the materials with

positive pressure coefficients is that they are all anisotropic. The AS2S3

samples are actually glasses, but crystalline AS2S3 is very anisotropic.

The majority of the materials were, for our purposes, well behaved,

i.e., the measured capacitances did not drift, the loss components were

small, and electrodes adhered well. There are specific classes of materials

which do not behave well: they are piezoelectric and pyroelectric crystals,

ceramics, and impure materials.

Table I Capacitance Data

Material Die! ectric

Constant ear* lt)12/Pa rar x io 6 /k

CaF2 6.8 -37.6 262.7

TjlCi, 31.4 -212 -355

TJlBr 30.3 -220 -320

KRS-5 32.0 -245 i -C* o BN, Pyrolytic 3.4 .121 -51

BN, Hot Pressed 4.5 62 140

Quartz

X-cut 4.5 7.7 -2.4

Y-cut 4.5 7.7 -3.5

Z-cut 4.7 -1.9 33.4

XLZ 45° 4.6 7.7 10.4

YLX 45° 4.6 2.8 20.4

Sapphire

(0001) 11 .5 -11.6 136.3

(1010) 9.4 -10.6 95.8

(1120) 9.5 -10.7 95.9

(1102) 10.0 -10.6 107.8

Lucalox 10.2 -52.8 146

MgF2 5.5 -13.26 172.3

MgF2 4.8 -21 ,13 199.4

MgF2 Ceramic 5.3 -21.6 215

Irtran 1 6GG (Gd 3 Ga 5 0 12 ) 12.6 -17.0 127

Table I (continued)

Material Dielectric i- x 10 12 /Pa f x 10 6 /K

Constant

C dP C dT

AS2S3

(Servo) 7.4 116 63.5

11 7.7 113 78.3

11 7.8 no 75.4

(Barnes) 7.7 114 66.4

Spinel (MgAl 2 0 4 ) 8.4 -12.5 135.3

Glass (NBS) 6.5 -22.5 139

Glass (UK50) 6.4 -34.3 236

Zirconate

Ceramic 34.4 -51 16.8

Cal cite 8.0 12.2 327.2

Cal cite 7.7 72.0 329.0

CaF2 -3%Er 3+ 5.6 -50.4 182

LiTa0 3 54 -47.1 165,6

LiTa0 3 44 -27.7 1302,5

BGO (Bi 1 2 Ge0 2 o

)

46 -102.7 73,5

Diamond 5.9 - 1.444 9.2

OfM a) t— 23 22.8 151.0

Te02 27 - 38.0 255.5

LiNb0 3 83 - 59.1 387

Li Nb0 3 29 - 6.8 734

13

The piezoelectric materials, quartz and BGO, both underwent long term

relaxations after pressure changes. Quartz was particularly bad in this

respect where large relaxations (40% of total change) were observed with

relaxation times of the order of a day. This was only true for crystals with

a component of the Z axis parallel to the electric field, the X and Y cuts were

well behaved. It may be significant that strain cannot produce a polarization

change along the Z axis in quartz, but this information does not lead to an

obvious explanation. BGO has similar effects but they are much smaller in

magnitude, this will be discuss more fully below.

Li Nb0 3 and LiTa0 3 are pyroelectrics, i.e. polarized ferroelectrics . The

samples were poled, single domain crystals cut parallel and perpendicular to the

axis of polarization. All four crystals underwent rather large relaxations

after temperature or pressure changes which went on for several hours. The

niobates were some two orders of magnitude more lossy than our normal crystals,

while the tanatalates were only about one order of magnitude larger.

The zirconate ceramic, Lucalox (A1 2 0 3 ceramic), and hot pressed BN were

both very lossy and drifted about continuously.

Impure MgF2 sampleshad a large loss component and a pronounced relaxation

in the capacitance. A poor quality BGO sample had much large relaxations than

did better quality samples.

We have had trouble getting aluminum to adhere well to the thallium salts,

BGO, and As 2 S 3

.

We have carried out a detailed analysis of the temperature and pressure

dependence of several samples which have' shown promise for use in a transducer.

Using a piston gauge for precise pressure determinations, measurements were

made at four different temperatures so that the cross derivatives of the

capacitance could be determined. The data were assumed to have the usual

functional form

C = C° (1 + AP + BP 2

) (1)
I
14

which rearranges to

ppr = A + BP. (2)

Accordingly, with the data plotted as AC/(PC°) versus P the quantities A and B

are determined, respectively, by the intercept and slope of the lines. The

plot for CaF 2 is shown as an example in Fig. 5. From these data dA/dT can be

derived, this quantity is required to determine the temperature dependence of the

pressure equation (Eq.l).

In Table 2 we have collected together data obtained in the above

fashion which is exemplary and will serve our discussion below.

Table 2. Temperature and Pressure Characteristics of Capacitor .

Material l d?

* 106/ K - Axl0 12/Pa g£x 10 12 /(PaK) B x 1

0

20 /Pa 2

CaF2 263 -37.8 -0.025 0.27

CaC0 3 ]_ 331.5 12.0 0.0149 0.42

CaC0 3 || 335 71 .0 0.0169 1 .25

AS2S3 76.7 110.6 0.030 -1.4

B60 (Bij2^S!02o) 73.7 -102.8 0.037 2.0

Table 3. Temperature and Pressure Characteristics of Pair Combinations.

Material J_ ffi-l x l o

6 /

K

R° dT

x 1 /K ArxlC 12 /Pa

dA

jp X 10 12/(PaK) B

r x 1

0

20 /Pa

CaC0 3 Pair 3.6 59.0 0.0020 0.76

BG0-As 2 S 3 3 213.4 -0.007 -1.2

15

The typical behavior of the pressure equations is that the coefficients A and B

have opposite signs, i.e. the capacitance changes less rapidly as the pressure

increases. This is not true of CaC0 3 and this may in fact be an early indication

the phase transition which occurs in this material at 1.4 GPa. For materials

with positive temperature coefficients A and dA/dT have the same sign, except

for BGO which appears to be unique in this respect.

16

PRESSURE RESOLUTION AND TEMPERATURE EFFECTS WITH CAPACITOR PAIR COMBINATIONS.

In our attempt at circumventing the temperature dependence inherent in

individual dielectric capacitors, we have been using a device where two

different capacitors, placed in opposite arms of the Wheatstone bridge measuring

circuit are both within the pressure vessel. The resulting bridge balance

gives the ratio of the two capacitance,

R = Ci/C2 (3)

The observed change of the ratio measurement as a function of

temperature or pressure is

1 dR _ 1 dCT 1 dC?

R dT C l dT " C 2 dT

and

1 dR _ 1 dC 7 1 dC 2 R dP "

C 2 dP “ C 2 dP

( 4 )

(5)

The appropriate capacitors combinations for use in this type of pressure

transducer are therefore, ones having nearly identical temperature dependences

but widely differing pressure dependences. It should be pointed out in Eq. 4

that it is the fractional temperature dependences of the capacitances that must

be equated, this is a property of the material and does not depend on the size

of the capacitance. What we need to find are pairs of materials, which in the

plot in Fig. 6, are displaced from each other along a nearly vertical line, but

are displaced by enough to give sufficient pressure resolution. Initially, no

appropriate combinations were known and we began our search by looking at

anisotropic materials. The capacitance along different axes in anisotropic

materials are usually quite different and intermediate values can be obtained

with samples cut at the various angles between the principle axes. This

17

approach did not directly produce any useful combinations but it did lead to

the combination of parallel and perpendicular cuts of calcite (CaC0 3 ) which

can be used as a pair in a pressure transducer. Subsequently a second useful

combination was found which consists of Bi 12 Ge0 2 o(BGO) and As 2 S 3

.

The data on the capacitor pair combinations can be analysed in the same

fashion as that of the individual capacitors given in Eq.l by writing

R = R° (1 + ArP + B rP

2

). (6)

This can be evaluated directly or from the data on the individual capacitors

ej and e2 as defined by Eq. 1, since

R = £4 (l + (Aj-A2 ) P + [(Bj-B 2 ) - AzCAj-Az)] P

2 +---) (7)

Similarly, the pressure and temperature derivatives of R leads to

expressions involving the differences of the corresponding terms for the

individual capacitors such as

1 dR 1 dR° , dA

r R dT ~ R° dT dT

1 dCT

Ci° 3T

] dC 2 + (

dAi _ dA 2

"\ C 2

° dT VdT dT / P + ...

( 8 )

and

1 dR

R dP

= A r + (2Br-Ar 2

) P

= (A,-A2 ) - [

2 ( Bj -B 2 ) — (Af A2 )] P +•••

(9)

Data for the calcite pair and the BG0-As 2 S 3 combination are given in Table 3.

The data obtained from the capacitor combinations agree with that derived from

the individual measurements using Eqns. 7-9.
.
In the introduction we stated that the resolution of a piston gauge at

pressures in the range of 70 MPa (10,000 psi) is about 1 : 1

0

5 or 700 Pa (0.1 psi

To be able to measure a pressure change of 700 Pa with a calcite pair transducer

requires that we be able to measure the fractional capacitance changes to the

following level.

1 dR

R dP

x AP = 59.0 x 10~ 12/Pa x 700 Pa = 4.2 x 10‘ 8

This value is within the resolution of our bridge of 1:10 8 but beyond the

stated accuracies of bridge ratio transformers, 1 : 1

0

7

. Vlhether non-linearities

in the bridge could be corrected for in the calibration procedure would have to

be determined. It should be pointed out that the pressure resolution of the

capacitance gauge is nearly independent of total pressure so that its fractional

resolution, AP/P, is better at higher pressures. With the piston gauge it is

the factional resolution which remains essentially constant except for the lower

end of its range where its precision drops off.

The temperature stability and accuracy which is required enters in three

different ways.

0) the two capacitors must be in thermal equilibrium with each other.

This depends not on the pressure dependence of the capacitor pair but

on the temperature dependence of the individual capacitors (which

by choice are nearly identical). The total temperature difference

between a pair of calcite crystals that would be equivalent to a

pressure change of 700 Pa is

1

R dP

1 dC

C dT

AP

59.0 x 10~ 12 x 700

333 x 10" 6 0.12 mK.

This is a small temperature difference but should be no difficulty

since the two capacitors will be in close proximity and symmetrically

located at the center of the pressure vessel

.
.
19

(2) The temperature of the capacitance pair for the determination of R

under pressure must be the same as it was for the determination of

R° at zero pressure. The allowable deviation of the temperature

between these two measurements depends somewhat on the pressure

measured. The temperature change that is equivalent to 700 Pa for

a cal cite pair is

1 dR

AP 59.0 x 10" 12 x 700

AT =

TFT5 dA

= i =11.5 + 11.0 m

+ HT

P 3 - 6 x 1°“ 6 + 0-002 x 10- 12 P

Where the range of values is for pressures between zero and

70 MPa. Thus the temperature can change by several millikelvin

during the pressure cycling and have no effect on the pressure resolution at the 700 Pa level.

(3) The final temperature effect arises from the temperature dependence

of the pressure coefficient and requires that the pressure transducer

be operated at the temperature at which it was calibrated. The

uncertainty in the absolute temperature or displacement therefrom

which will cau.se an uncertainty of 700 Pa in a pressure determination

of 70 MPa is

dT

59.0 x 10" 12 x 700

0.002 x 1

0

-12x70xl

0

6 = 295 mK.

The inverse pressure dependence makes this restriction more strigent

at high pressures.
-
I Ml

20

These results show that a practical pressure transducer could be made

from a pair of calcite capacitors. The pressure resolution may be considered

marginal even though it is 50% greater than the CaF2 transducer originally

considered, but the thermal requirements are very reasonable and could be

easily met. The real drawback i> that .the crystals are yery fragile. The

material is hard but it cleaves rather easily. We had no trouble with these

crystals in our research apparatus, but in the prototype transducer (see below)

we have repeatedly broken crystals. The problem appears to be due to poor oil

flow through the sample holder which lifts the crystals off their contacts. The

holder has been modified to correct this but not tested.

The temperature and pressure dependences of the BG0-As 2 S 3 combination show

it to have great potential. The pressure dependence is 3.6 time that of the

calcite pair so that it should be possible to resolve 70 Pa (0.01 psi ) with

this pair and to have known accuracy at the 700 Pa (0.1 psi) level. The thermal

requirements with the BG0-As 2 S 3 combination are listed in Table 4 with those

for the calcite pair. Comparison shows the large improvement that could be

achieved with this combination.

Table 4. Thermal Stability Required to Obtain 700 Pa(0.1 psi)

Pressure Resolution with a Calcite Pair and a BGO - As?S 3 Capacitor Combination .

'.s • Thermal Equilibrium Short Term

Material s Between Capacitors Temperature Stability

At 0 Pa At 70 MPa

Long Term

Temperature Accuracy

At 70 MPa

CaC0 3 0.12 mK 11.5 mK 11.0 mK 295 mK

BGO ~ As 2 S 3 2.0 mK 50 mK 63 mK 305 mK

The drawback with the BG0-As 2 S 3 combination is with the BGO crystals.

This material is piezoelectric and as already mentioned, such materials have

large relaxation effects after temperature or 'pressure changes the reason

for which is not known. Our initial sample of this material was of poor

quality, it was opague, and showed large relaxations. A second set of samples

were of much better quality and were optically clear. These crystals still

showed relaxation effects , though much smaller than before and also showed some

discontinuous effects. When samples were repeatedly pressure cycled to 140 MPa,

the capacitance ratio would return to its zero value several times and then

shift to a new value, displaced by upwards to the equivalent of 7000 Pa (1 psi).

The shifts were nearly always in the same direction. When the cell was held at

pressure for a period of time the capacitance would drift slowly to higher values,

then when returned to zero it would relax back to its initial value over a

period of hours.

We do not know the cause of this behavior, but we suspect it is due to

crystalline imperfections, dislocations or possible impurities, causing

strain in the crystals. This is important in piezoelectrics but not in ordinary

crystals since the strains will effect the bulk polarization and therefore

the polarizability. Because of the attractiveness of this material as a

transducer we are purchasing more crystal, of presumably higher quality, to

see if they will be better behaved. Crystals of three different orientations

are going to be tested to see if there may be different behavior in the

different directions as in quartz. This is not to likely since BGO is cubic

and the piezoelectric constant is isotropic, but it is worth the effort since the

cause of the problem is unknown. There is a possibility that the problem with

BGO may be with the coating for we have not been able to get aluminum to adhere

well to it. This is also true of As 2 S 3 but we have found no adverse effects
'
22

with this material. During the more than one hundred pressure cycles the

BG0 -As 2 S 3 combination was put through the As 2 S 3 capacitance always returned

to the same value.

23

Adiabatic Heating and Transducer. Thermostating .

The simplest way to thermostat a system is to isolate it as well as

possible from the surroundings and to minimize any disturbances that would

tend to change its temperature. The thermostating of the pressure transducer

is complicated, however, by the adiabatic heating effects which occur whenever the pressure is changed. When the pressure transducer is pressurized,

all the material inside the pressure vessel (the samples, sample holder,

and pressurizing oil) are under compressive stress and increase in temperature.

The pressure vessel itself is placed under a net tensile stress when the

pressure increases and, as a result, it cools. The reverse occurs when the

transducer is depressurized. Consequently, in thermostating the transducer

one would need, in general, the capability of both heating and cooling the

system. Also, with part of the system warming and others cooling, a

rapidly-responding thermostat would probably prolong the period of equilibration.

We have managed to get around this problem by equating the heating and

cooling that occur within the transducer during any pressure change, so

that there will be little or no temperature change when thermal equilibrium

is reestablished.

The amount of heating that occurs in a piece of material under compressive or tensile stress is given by

Q

= TVftAP

,

where 3 is the average thermal expansion coefficient for the range of the

pressure change, AP, and V is the average volume.

24

The cooling that occurs in the pressure vessel itself (see Appendix),

when it is internally pressurized , is equal in magnitude to the amount of heating

that would occur upon externally pressurizing a piece of steel of the same

composition as that of the vessel and having the same volume as the internal

volume of the vessel. In other v/ords, if we could completely fill the inside

of the vessel with a steel plug and then pressurize the system using a negligibly

small amount of oil, there would be no temperature change when equilibrium is

reestabl ished.

For steels such as that of the pressure vessel, the thermal expansion

coefficient is about 55 in units of 10~ 6 /K. The paraffin oil we have been using

as a pressurizing fluid has a coefficient of about 750. Since we must have at

least a small quantity of oil in the transducer, we need to offset its large

coefficient by including in the pressure vessel a large amount of material

with a thermal expansion coefficient smaller than steel. Fortunately, there

is a suitable material. Invar, a high nickel steel, that has a thermal expansion

coefficient of only 3.6 units. By limiting the volume of oil in the pressure

vessel to about 1% of the total yolume (12 cm 3

) and filling the rest of available

volume with Invar, we calculate that temperature changes can be kept at a

negligible level. The heating effects cannot be eliminated completely because

the oil is highly compressible so that its expansion is a marked function of

the pressure.

For the prototype pressure transducer we are using a commercial (High

Pressure Equipment Company) pressure vessel with a pressure rating of 138 MPa

(20,000 psi). The vessel has a 3.8 cm (1.5 in.) I.D. and a depth of 15 cm (6 in.)

and comes with a pressure connection in the bottom of the vessel and one in the

center of the one-piece threaded closure. We have modified the closure with three

additional pressure connections to allow for the separate entry of the three

electrical feed-throughs required for the capacitance measurements.

25

An Invar sample holder has been fabricated which attaches to the bottom

of the pressure closure and effectively fills the entire volume of the pressure

vessel. The sample holder, diagramed in Fig. 7, was made from six 6.3 mm (% in.)

plates, which, when bolted together, form the cylindrical plug shown on the left.

The central two pieces hold the low voltage electrode, which is common to both

capacitors, and the capacitors themselves fit into recesses on the outside of

these pieces. The next two pieces hold the high voltage electrodes, which make

contact with the back of the capacitors. The three electrodes are made from

small gold-deposited bellows, the same as used in our experimental system. The

position of two outer electrodes can be adjusted to ensure sufficient force on

the contacts for electrical continuity. The outer two plates simply fill out

the volume. A picture of the partially disassembled sample holder is shown

with the pressure vessel in Fig. 8.

Our experiments indicate that the ideas incorporated in this device are

basically correct. In Fig. 9 we show the actual temperature change observed

with the system upon changing the pressure. The pressure vessel was effectively

isolated from the surroundings in an insulated container with a thermometer attached

to the outer surface of the pressure vessel. At the center of the figure is shown

the effect of depressurizing the vessel over about a 1 minute period from 140 MPa

(20,000 psi) to zero. The outer surface of the vessel first warms, but as the

vessel thermally equilibrates with the material i ns i e, it cools, stopping at a

temperature 4 mK below the initial temperature. To the right is seen the reverse

effect when the system was repressurized. The slope of the base line in the

figure is due to the small loss of heat .to the surroundings. We calculate that

each cm 3 of oil in the system that is displaced by invar will produce a 3 mK

difference in the temperature change observed with a 140 MPa pressure change.

The results in Fig. 9 indicate that 1 1/3 cm 3 more oil needs to be displaced from

the system to exactly balance the heating and cooling effects. To get to this

26

point it was necessary to displace much more oil than predicted by the calculation.

In Fig. 1_0 we have plotted the temperature changes observed with three different

quantities of oil in the system and find that the temperature changes are varying

as predicted but are displaced from the calculated curve by nearly 8 cm 3 of oil.

Although it is not easy to determine the exact amount of oil in the system, (considering screw slots, counter sinks, oil equivalent of the O-ring seal, etc.) we

do not think we are in error by this amount. The volume differences between the

plotted points in Fig. 10. are accurately known, however, for they were determined

by the volume of the invar pieces used to displace successive quantities of oil.

A possible cause of the discrepancy is our failure to properly account for the

heating effects of the threaded vessel closure; our calculation assumed that the

vessel has spherical ends. A more likely cause is that the expansivity values

we used for the materials involved are badly in error. This is unfortunate for

in designing the sample holder we were overgenerous in the size of the openings

allowed for various purposes and the pieces will be difficult to modify.

We have shown earlier that for the capacitor combinations (calcite-pair or

BGO-AS2S3 combination) we are considering, the change in temperature which can

be tolerated at different pressures is in excess of lOmK. With the Invar sample

holder the changes in temperature that occur when the pressure is changed will

be considerably less than that value. As a result, there is no need to actively

thermostat the pressure vessel itself, but to thermostat only its surroundings

§0 that the temperature of the vessel stays within prescribed bounds.

The thermostating arrangement to be used will consist of placing the pressure

vessel in a highly conductive container but insulating the vessel from the container so that the thermal relaxation time will be tens of minutes. The container

itself will then be well insulated from the surrounding and regulated at about

35 °C , well above room temperature. Since the conductive container will be well

27

insulated from all disturbances its regulator can be rather unsophisticated. The

pressure vessel will require a separate thermometer to assure that it is within

the prescribed temperature range as well as an auxiliary heater to bring it

initially to the thermostated temperature.

28

AUTOMATIC CAPACITANCE BRIDGE

A limited-range capacitance bridge has been constructed which was designed

specifically for use with the dielectric capacitance pressure gauge. It is

capable of measuring the ratio of two capacitors which differ by less than 10%

and which also have reasonably small loss tangents. After an initial adjustment,

the bridge operation is completely automatic.

The design of the bridge proper, shown in Fig. 11, is in principle the same

as that being used as a research tool in our laboratory. The bridge transformer

forms the 1:1 ratio arm of the bridge and supplies the voltage for the ratio transformer used in balancing the bridge. The output voltage of the ratio transformer

is injected into one of the ratio arms of the bridge through the two stage transformer. The power for this injected voltage comes from an operational amplifier

so that there is no loading of the ratio tranformer and the bridge impedance is

kept small. It is the turns ratio on the two stage transformer and the voltage

supplied to the ratio transformer that limits the range of capacitor ratios that

can be measured. A switch on the primary of the two stage transformer allows the

selection of a total range of either 1 or 10%. The switch on the input to the

ratio transformer allows this range of bridge ratios to be taken on either the

positive or negative sides or centered about the ratio of 1. Any difference in

loss between the measuring capacitor and the reference capacitor is compensated

by injecting an in-phase, i.e. resistive component, signal into the detector arm

of the bridge. The magnitude of this signal is controlled by multiplying the

D.C. in-phase signal of the phase sensitive detector by an A.C. signal from the

bridge transformer.

Fig. 12 is a block diagram of the logic circuitry for the automation of the

capacitance bridge. The design was limited to some extent by the incorporation

of a 5 decade programmable ratio transformer (PRT) . ye require a 7 digit reading

29

and would desire 8 digits, so it is necessary to limit the range of capacitance

ratios that the instrument can cover. In the 1% range the first two significant

digits are preset by the range control, in the 10% range only the first significant digits are determined by the ratio transformer and two additional digits

are obtained by the digital conversion cf the analog voltage resulting from any

remaining bridge imbalance.

In operation the imbalance current from the capacitance bridge is amplified

by an FET preamplifier and by three programmable gain amplifier sections. The

FET preamplifier goes directly on the pressure transducer thereby reducing the

effects of lead capacitance on the bridge. These are followed by two lock-in

amplifiers, one phased to detect the resistive loss component of the bridge and

the other phased at 90° to detect the capacitive imbalance. The rectified loss

component is further filtered and used to control the automatic loss feedback

network in the bridge. This signal can be monitored through a front panel BNC

connector

.

The rectified capacitance imbalance signal is fed to the gain control module

and to two voltage-to-frequency converters (VFC) . The signal is inverted before

one of the VF'C, so that one VFC delivers a pulse rate proportional to positive

signals and the other tc negative signals.

The output of the t^o VFC’s are fed into a bank of 14 up-down counters by

way of a multiplex unit that switches in and out various counters. After each

period of counting the contents of the counters are dumped into latches which

hold that count while the next is in progress. The signals from the latches

are routed through buffers to the BCD output for external processing and are

routed to the seven-segment decoders which generate a 10 digit seven-segment

incandescent display. The signal from latches 4’, 5, 6, 7, and 8 are routed

through drivers to the programmable ratio transformer and provide the undated

bridge setting. Only decades 9 through 13 are zeroed before each count so that
'

-
30

the new count is added to or subtracted from the existing transformer setting.

The clock steps down the bridge frequency to approximately 10 second and

1 second intervals which are used as counting times. The clock is used to turn

the counters on and off, and while the counters are off enables the gain control

and range control, transfers information from the decade counter to the latches,

zeros counters 9 through 13 and turns on the counters for the next interval.

The gain control looks at the output of the bridge and sets the amplifier

gain decades to keep the input to the VFC's less than 10 volts but greater than

1/2 volt. It is operative only when the counters are off. When the amplifier

gain changes the counting gain or count time must change to keep the overall

gain constant. The counter gain is changed by the multiplexers switching between

the last five decade counters. On the highest amplifier gain the clock is set

for 10 second counts; on all other gains it is set for 1 second counts.

The range control switches between the following deviation capabilities of

the bridge: 0 to 1%, + 1/2%, -1 to 0%, 0 to 10£, + 5%, and -10 to 0%. The switching

is done automatically seeking the highest sensitivity. Range control switching

takes place only when the counter is off and only when the programmable ratio

transformer is asked to go beyond its limit (as detected by a carry of borrow

signal from counter 4’). Counters 1, 2, 3, 4, 4' are reset each time a range

control switching occurs.

Decade counters 9 and 10 do not control the bridge. They are zeroed before

each count and provide the two analog decades of bridge sensitivity beyond the

ratio transformer setting.

The fourth decade is split, 4 going to the readout and 4' controlling the

PRT. This was necessary to permit the- use of the bridge ranges + 1/2% and + 5%.

On these ranges, when the bridge ratio (and readout) is exactly 1.000, the PRT

must be set to 50000, the 5 appearing in the fourth readout decade.
*

'
31

The precision desired from this bridge, 1:107

, is pushing the limits of

the programmable ratio transformer. These devices are frequency dependent, the

ratios depending to some extent on winding impedance, core size, shut capacitance,

etc. The ratio transformer was designed for 400 Hz operation but we would like

to work at a higher frequency and had intended to use 1592 Hz (m = 10 4 ), the

frequency of our research bridge. The NBS Electrical Measurements Section has

determined the accuracy of the ratio transformer as a function of frequency to

establish the size of the errors involved; the results are shown in Fig. 13.

Ratio settings of 0.2, 0.5, and 0.8 are plotted versus frequency squared.

Theoretically, errors in ratio settings reach maxima at the 0.8 settings plotted in

the figure.

We decided to operate the bridge at 1,000 Hz where the accuracy of all ratios

is within 2:10 , and, in addition, the ratios all err in the same way exoept for

the two lowest settings. We have tested the bridge to a limited extent in our

laboratory and believe it to be measuring with a precision approaching 1:10.

The bridge has been shipped to Redstone Arsenal for further testing which will

include an evaluation of the effects of temperature, humidity, and vibration.

The bridge circuits are completely documented in a way which should facilitate

their reproduction. Complete blue prints have been maintained and, in addition,

wiring locations have been put on punch cards. Print-outs of different sorting

sequences of the cards have been valuable aids in both the original wiring and

in trouble-shooting.

The basic design and construction of this capacitance bridge has been

primarily due to the efforts of Robert S« Kaeser of this laboratory.

32

CURRENT DEVELOPMENTS

We are continuing to look at any material we can acquire in order to get

more capacitance data and possibly find other useful transducer materials. As mentionei

above, we are continuing to look at samples of BGO in the hope that the observed

instabilities may be only sample dependent. Since the resolution of capacitive

transducer is esseatually independent of pressure it is ideal for measurements

at high pressures. For this reason we are extending our experiments to 700 MPa

(100,000psi) to see how the capacitance gauge will operate in that range. At

these higher pressures piston gauges become less accurate because of fluid

viscosity problems. These problems should not effect the capacitive transducer

so there should be little trouble achieving potential accuracies in excess of that

of the piston gauges. We see no reason why the calcite pair combination can not

be used to these higher pressures since it does not undergo any phase transitions

until 1.4 GPa (200,000psi)

.

33

APPENDIX

Cooling of a Pressure Vessel upon Pressurization

The isothermal heating which occurs in piece of material under compressive

stress can be calculated by writing the formula (see M. W. Zemansky, Heat and

Thermodynamics , 5th Ed., p.288)

Where 8 is the volume thermal expansion. This can be written in a more

general form as

volume dV. a = 1/3 8 is the linear thermal expansion coefficient. Shear stresses

are neglected.

The individual stress components for uniformly shaped pressure vessels under

internal pressure, P, can be calculated using standard formulae as given by R. J.

Roark ( Formulas for Stress and Strain , 4th Ed., p. 308).

As a practical example we consider a cylindrical vessel with spherical ends.

The internal and external radii are a and b and the stresses at a point r in the

vessel wall are given by:

(Al)

(A2)

dS = ZdS_^ is the sum of the three components of the stress acting on the

Cylindrical Portion -

longitudinal stress

34

hoop stress

ds . . liibV) dp>

r

2 (b 2 -a 2

)

radial stress

dS 3 - + &&& dP,

r

2 (b 2 -a 2

)

Spherical Ends -

hoop stresses

dSx = dS 2 =

_ a

3 (b 3 +2r 3

) 2r 3 (b 3 -a 3

)

dP,

radial stress

ds, = + S

9

. (b 3J

3

) dP . r

3 (b 3 -a 3

)

The contributions of the individual stress components can be found by

multiplying by the appropriate volume element, 27Trdr for cylindrical segments

and 4frr 2 dr for spherical segments, and integrating over r from a to b.

The total contribution is, however, more easily found since the sum of

the three components of both segments are independent of r.

dS = - 3 (— ) dP cyl

b

2 -a 2

and (A3)

dS = - 3 (— ) dP

sph

b

3 -a 3

The volume integrations of Eq. A2 can now be carried out separately

giving

V = u£(b 2 -a 2

) cyl

and (A4

)

V = 4/3 iT(b 3 -a 3

) sph

3b

Multiplying the appropriate parts of Eqs-. A3 and A4 and substituting in

Eq. A2 we have

- Q

= T /

3 a(7ra 2 £ + 4/3TTa 3

) dP

The expression in parentheses is just the internal volume of the vessel

so we can write

Q

= T Jg V

±dP

This is just the expression for the compression heating by the pressure

change dP of a volume V_^ with thermal expansion g as given by Eq. 1A but with

the sign changed.

FIGURE CAPTIONS

1/ Capacitance Bridge.

2/ Electrode Configuration on Samples, Masking Rings, and Coating Arrangement.

3/ Sample Holder.

4/ Five Sample Holders Mounted on Pressure Vessel Closure.

5/ Pressure Dependence of a CaF 2 Capacitor at Four Temperatures.

6/ The Pressure Dependence of the Capacitance of Various Materials as a Function of Their Temperature Dependence. The temperature dependence is

the atmospheric pressure value and the pressure dependence was determined

at 35 C. The lines shown, join the values measured parallel and

perpendicular to the crystalline axis of anisotropic materials and represent temperature and pressure dependences that could be realized for crystals

cut at intermediate angles.

7/ Invar Sample Holder. The holder is shown assembled on the left and disassembled on the right. The holder is 1 1/2 inches in diameter and 6

inches long and fits snugly in the cavity of a commercial pressure vessel.

The dielectric capacitors fit into recesses in the inner two plates and

. the electrical connections are made using small bellows as spring contacts.

8/ Invar Sample Holder and Pressure Vessel.

9/ Temperature changes at the outer surface of the isolated pressure vessel

resulting from 140 MPa (20,000psi) pressure changes. The Vessel contains

the Invar sample holder and about 5 cm 3 of pressurizing oil. The central

peak is for decreasing the pressure to zero and the peak on the right is

for repressurizing.

10/ Net temperature changes in the isolated transducer system as it is pressurized to 140 MPa (20,000psi) while containing different quantities of oil.

11/ Automatic Capacitance Bridge.

12/ Automatic Capacitance Comparator.

13/ Ratio errors as a function of frequency in programhble ratio transformer.
,
&

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(MPa)





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