DE6908118U - DEVICE FOR DETERMINING POLAR LIQUIDS - Google Patents

Description

Case A-61

O.l.P. 525

IiATIONAI LEAD COMPANY New York, Ii.Y. / USA

Device for determining polar liquids

The invention "relates generally to a device for Determination of polar liquids. In particular "concerns the Invention of ferroelectric or ferrielectric crystals with separate electrodes that contain various additives and, in connection with the electrodes, capacitance properties exhibit.

The device according to the invention can be suitable for all applications in which detection of the occurrence of "certain polar liquid vapors is desired. For example, the device for detection" or can be used to determine the moisture content of the surrounding air, which can be connected to a suitable electrical circuit to determine the moisture content or to operate a device for moisture content. The invention can also be used in many other areas, for example for the detection of polar liquid vapors from sole when prospecting for oil. In addition, many are accessible to the expert

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other areas of application of the invention. For example, the invention can be used in the medical and biological fields as well as in manufacturing and process engineering or process control, for example in chemical processes or similar.

Known devices for measuring moisture need numerous different arrangements. Typical of such devices is the use of hair, Strings or threads and the like to make a suitable connection. There were also electrical circuits used in which a resistance of the circuit with an organic, on the humidity of the ambient air can be provided with an attractive coating.

These known structures for measuring or determining the moisture have proven to be unsatisfactory because the individual elements, especially hair, strings and the like, could break or other physical Could be exposed to damage. These structures were also unsatisfactory because the results obtained were not sufficiently reliable.

With the aim to develop a robust and reliable elements for the determination of polar liquids, .gemäß the invention has been an apparatus for detecting "'■ tzvt for the determination of such polar vapors which gekennzeichnet-

is through a ferroelectric or ferroelectric see

j crystal that is used to improve bz;?. Enlargement of his

f occurring under the influence of polar fluid vapors

electrical properties provided with at least one additive is and at least z ^ has separate electrodes, steep the ΐώΐ de-2 crystal in contact. The erfindusgsges-ä-Ee Device is reliable because the crystal is after je-dex Yerwendurig always returned to its original state. O

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As described in more detail below, is the structure of the device is particularly sensitive.

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The term "ferroelectric crystal" as used herein is said to be a crystal with ferroelectric properties mark. For example, the crystal has a Curie point and its polarization can be reversed by a voltage whose amount is less than the breakdown voltage of the crystal. A typical example of such a crystal is barium titanate. The term used here "Ferroelectric crystal" is also intended to be ferrielectric Crystals include, such as wisnmttitanate, the like have characteristic properties v / ie ferroelectri- see crystals and also include a field that can be switched by a certain threshold value if the host direction the applied voltage is reversed.

The invention is based on äex theory that the crystal material numerous areas and crystal domain walls will move to Y / eist. Around the crystal area walls, the crystal surface consists of two oppositely polarized areas that are separated from one another by the crystal area wall. Normally, the crystal surface will attract enough charges from the environment that the surface charge appears to be essentially neutralized. If, on the other hand, vapors of polar liquid, such as moisture and the like, reach the crystal surface and the electrodes connected to the crystal are additionally impressed with an alternating field, the interaction of the field areas and the dipole field of the polar vapor results in the capacitance of the Crystal (which has capacitance properties in connection with the assigned electrodes) changes depending on how much polar vapor is deposited on the crystal surface *

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In addition, the "resistance between the two electrodes changes depending on the deposited en quantity polish Plüssigkeitsdampfes. Although the exact physical Yorgänge this phenomenon are not clear ₅ could v grounded determined / that as the main factor for obtaining a high-sensitivity Naehweismittels the interaction of the electrodes from an electric field imposed by a voltage source, the crystal regions mentioned above, the level of polar molecules, and the presence of certain specific additives in the crystal also play a role.

Although quite a number of ferroelectric crystalline Materials have been identified that are sensitive to the presence of polar molecules, such as moisture in the form of water vapor or the like, respond by changing the capacitance and / or resistance of the detection medium, with the electrical device arranged on the associated crystal

, which is provided, it turned out that / with bismuth titanate A particularly strong effect can be achieved, presumably because of this, because this material has a pronounced effect Threshold value switching field (electrical remanence field, the only can be switched by a certain threshold voltage can) and has a stable range configuration.

Bismuth titanate has a very high Curie temperature, approximately approximately 675 ° C. For this reason, capacity and changes in resistance of the detection or determination or measuring devices depending on the temperature practically negligible. Accordingly, lets Such a device can not only be used as an instrument that measures relative values, but rather allows it to be used Calibrate measurement of absolute values. As explained in more detail below, the changes in capacitance and resistance can be determined the determination device with the help of a suitable electrical circuit measure <>

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The presence of a visual threshold switch panel in bismuth titanate enables a relatively high control voltage to be applied or maintained without a The areas are switched over. This is one of the reasons why the results that can be achieved with Wisinuttltanatkrlstallen Extraordinary are other crystals that have a welding value switch panel and also good results supply are sodium potassium niobate, uatriuinniobate— vanadate, lithium miobate and barium natrluzi-niobate.

The presence of certain additives in the crystal and the interaction of the ferroelectric or ferrielectric Areas with the PeId applied to the electrodes of the device are in the presence of polar molecules the main factors in achieving strong responsiveness,

Grown or pulled crystals with certain additives, as explained in more detail below, show extraordinary strong changes in their dielectric (capacitive) and conductivity (resistance) properties, if they are exposed to polar liquid vapors.

Such additives in the crystal obviously act like catalysts in chemical processes, as it could be clearly determined that the presence of certain additives denotes the Crystal responsive to certain, in polar liquid vapors makes existing chemicals.

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It was also determined ₃ that the detection device has its maximum sensitivity or responsiveness if the control alternating voltage applied to the electrodes of the detection device is smaller, but almost as large as the negative voltage of the device and is not too high. a value is held that does not yet switch the range configuration of the crystal »

It has also been determined that a specific frequency results in an optimum sensitivity for a certain Uaehweisvorrich- Maintenance, depending on the additives contained uarin or the type of are to be determined or detected _a vapor Typical operating frequencies in the range of 20 to 500 kHz, good results however, were also achieved with slightly higher frequencies.

The detection or measuring device must also be constructed so that the free crystal area of the part of the crystal to which the electrodes are attached is large in comparison with the electrode area. If the electrodes essentially cover the entire crystal surface, then the initial or antavirus magnitude that can be achieved with the each device is practically zero. It was found that the free crystal surface must at least correspond to the ratio C / C or G / G defined in more detail below _; , and in general the free crystal area should be at least ten times larger than the electrode area. Experimental devices which did not have the correct ratio between free crystal area and electrode area did not show satisfactory sensitivity during the measurements. Among other things, to make the surface of the electrodes highly effective, it was additionally determined that their outline or external dimensions should be large. "

The objects of the invention are to provide a new device for the detection or determination of polar Liquid vapors used for measurement or control moisture, or for the detection of certain polar liquid vapors, such as hydrogen sulf it and the like, which occur in crude oils, with the device when tracing or de Evidence of an existing drilling oil source can be used. This will make it possible to use fewer test holes to drill deeper than was previously necessary to detect any oil present in a certain drilling area was. The structure of the device according to the invention is very simple and cheap, but at the same time it is also very compact and versatile in use. Besides that is the detection device in many different areas, such as etv / a in the control of chemical processes, applicable.

Further goals and advantages of the invention are explained in more detail below with reference to the drawings, for example *

g gii cxiic Tuiucicuiaiuuii cxiicr ex i

Detection or determination device, the Area walls in the crystal that have oppositely polarized surfaces on each side, are shown schematically;

Fig. 2 shows the plan view of a modified embodiment the invention;

Fig. 5 shows the plan view of a further invention. appropriate execution form;

4 shows a longitudinal section through yet another embodiment according to the invention;

The following figures show two corresponding application examples of the method according to the invention.

I 4 * I I I ·

Fig. 5 shows a schematic circuit diagram of an electrical Circuit that has a detection or determination device according to the invention contains;

Figure 6 shows a partial utilizing the invention _; schematic circuit diagram of a further circuit; and

Fig. 7 shows a schematic circuit diagram of still another electrical circuit that the inventive device includes »

A first embodiment of the invention is illustrated in FIG. 1, a ferroelectric crystal being designated quite generally by the reference numeral 10. This crystal comprises a single-crystal platelet which can consist of one of the known or above-mentioned ferroelectric and / or ferrielectric crystals. In the preferred embodiment, the crystal consists of bismuth titanate and, as mentioned, has a relatively high Curie temperature. The connections are formed by a pair of electrically conductive electrodes 12 and 14 which are in contact with the opposing faces of the crystal and are suitably attached. The electrodes can have a conductive oxide deposit produced in a known manner. In a typical embodiment, the thickness of the crystal 10 may be about 0.05 mm (2 mils) with a length of about. 6.4 mm (2/8 inch) and about 3 ₃ 2 nsn (1/8 inch) wide, while the diameter of the electrodes can measure about 1.6 mm (1/16 inch) and as generally circular disks are upset. In F15. 1 the length and thickness of the crystal are exaggerated - the electrodes 12 and 14 are suitable electrical conductors Όζώ. Feeders 16

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i I

! 3

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and 18 connected to the device with an associated to connect electrical circuit »

The illustrated crystal has a number of schematically illustrated area walls, denoted by the reference symbol 20 are marked. The crystal surface shows how illustrated by positive and negative markings on adjacent surfaces, a number opposite polarized surfaces, the adjoining oppositely polarized surfaces are separated from each other by the area walls. Beat up As described above, if vapors of polar liquids settle on the crystal surface, the capacity changes of the capacitor formed by parts 10, 12 and 14 as a function of the amount deposited on the crystal surface Amount of vapor of polar liquid "

/ The mode of operation of the determination or detection device appears to correspond to a mass spectrograph which generally responds to polar liquid vapors. It should be noted, however, that the determination device according to the invention has a much simpler structure than other devices that serve a similar Zv / corner. It can be seen that the change in capacitance and resistance of the crystal is to be regarded more as a surface effect, which is essentially more on the free crystal surface, which is not covered by an electrode, takes place than in the bulk of the crystal, the time-delayed response sensitivity of the measuring device, especially for polar liquid vapors, occurs relatively quickly, e.ii. according to Eirsva 5 minutes.Among other things, Wisiauttitanai shows a very high sensitivity to polar plush vapors and especially for (air) unrepentant when hafnium, chromium, uiobium salts are used in small amounts, ie in the range of e "twa

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0.05 to 3 moles are included so will give optimal results achieved. The amount of additives should be in the extremely large range of about 0.001 to 10 mol- ^ "

An alternating voltage is applied to the electrodes 12 and 14 via the conductors 16 and 18, with a Frequency of about 185 kHz resulted in optimal operating conditions when the additives contained tantalum, while with a frequency of about 30 kHz, optimal conditions were achieved when the additives hafnium, chromium or niobium exhibited.

It has been found that best results are obtained then when the activation temperature of the electrodes is about 400 ⁰ C and 12 fourteenth However, if electrodes with significantly higher activation temperatures. are used, a special heat and field treatment is necessary to regain the desired sensitivity. This heat treatment requires that the entire crystal arrangement is ^{brought to a temperature of around 400 to 5CC 0} C for a period of about 5 to 10 minutes, which is a characteristic ferrielectric transition.

at bismuttitas

ismuttitasät was determined.

The ratio of free crystal surface to the electrode surfaces before should be in the above range ,, in which case the free crystal surface is the entire Pläehe with

Corresponds to the end faces of the crystal provided with electrodes, ; which is not covered by the electrodes. The slektro—

The external stress should be in the ranges described above. In particular, it should be smaller, but close to the same size as the coercive clamping of the crystal, _etc.

In order to achieve the desired results , certain additives are - as mentioned - included in the crystal, Table I illustrates the results obtained with the various additives contained in Yisauttitanatlcristallen.

Table I.

HO-Pre nios Linseed oil ver G / G
5 Oleic acid G / G
S. Dimethylformamide G _s / G It she G _s / G _ group häli. G / G conditions Conditions Conditions !acid- - C.
S. C / C
S. C / C 1 1 c _s / c 7.6 Conditions 5.6 Μ « G 3 1 1 1 CVC 15th Sr 23.5 8.2 1 1 _ 14th _ _ Ba 1.3 8th 1 1 1.3 neglect 36 gbar.e effect _ Y 9 15th _ _ - _ _ 2.3 _ - La 15th 7.5 - - - - 8.8 Zr 10 9 - - - _ - - 81 Kf 3.4 4.2 _ _ _ - _ 5 Pb 4.2 8.5 - _ - - _ 12.5 V 1.5 16 did* - _ - 18th Kb 3.1 5 - - - - _ - - 2.8 Sb 3.5 50 1.2 - 1 2.6 15th 11.4 Tn 2, p 7.5 1.3 - 1 - 2.8 1.3 16 Cr 17.5 18th 1 1 1 1 3.6 1 1.3 Ko 1.4 1 1 1.6 1 1 1.3 3.7 2.3 Te 1 6th 1 1 1 1 1.2 2.4 2.8 W. 1.4 4.2 1 1 1 1 _ 7th Mr 1.9 2 1 3.2 1 1 1.4 25th 2.7 Ce 4.4 x, 2 1 1 _ 1 _ 7.5 1.5 Sm-Gc 1.2 6th 1 1 1.5 Gd 1.1 1 1 1.1

The first column of the table, labeled "Group", specifies the various elements that are used as additions in the i? Is— muttiatanat crystal are included with their usual chemical symbols are marked «

The next column illustrates the ratios achieved when the polar liquid vapor contained water. The next column shows the results when the

^% polar liquid vapor consisted of linseed oil, while the

the following columns indicate the ratios achieved, when the polar liquid vapors from oleic acid, dimethylformamide and acetic acid passed.

It will now be explained what the specific meanings of the ratios indicated in the vertical columns. For the first The ratio designated as C / C: C is the capacitance of the

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in Pig. 1 when the polar liquid vapors precipitated from the ambient air correspond to a moisture content of 100 ⁰ Jo . C corresponds to the capacitance of the capacitor illustrated in FIG. 1 when the surrounding air from which the polar liquid vapor is precipitated contains essentially no moisture. It turns out that the results differ considerably depending on the special elements contained as additives in the crystal and also depend on which particular polar liquid vapor is to be determined or determined.

In the table, the values G / G are given as the second ratio. G corresponds to the spec. Resistance of the capacitor shown in Fig.1, vvenn the polar liquid vapor ^{corresponds to a humidity of 100 c} /> , while G the spec. Resistance value indicates when the polar liquid vapor is essentially free of moisture. For both specified ratios it applies that the alternating voltage of the

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Bestlsssungsvorrlehtung when the electrodes are fed «. The values obtained are obtained from exposure to temperature and in air warmed to room temperature. 3) 1e Additives included in the crystal were in the range from about 0.001 to 10 l ole-fo in terms of quantity. Looking at Table I, it is easy to see that the polar fluid vapors have a pertinent effect on the dielectric and resistive properties of ferroelectric or ferroelectric crystals. It also shows that certain *. Additives increase the capacity variability, for example strontia, xanthan, zircon and |

Chrome. Other additions, on the other hand, increase the resistance - I. Variation nipfIndlchkeit j e.g. lanthanum, 2ίΙοΐ>, tantalum J and molybdenum. In some! Cases the! Two effects are about the same .. In! Some! Cases, the sensitivity dominates if there is a change in resistance. In other cases the sensitivity to the change prevails capacitive effect.

Table I illustrates how this effect can be used to measure and control moisture, for example when certain Y / isimrttltanatkrlstalle have such additives as zirconium, hafnium, uiobium and tantalum which are particularly suitable. When choosing the additives, the response sensitivity, i.e. the response size, and also the response time must be taken into account, which is generally about 5 minutes, while for more responsive additives, such as chromium, the response time is about 20 minutes, which corresponds to a relatively slow response behavior.

Table I also shows that other polar liquid vapors with certain contained in bismuth titanate Additions excellent sensitivity and response values

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result. For example, manganese in a bismuth titanate crystal ¹ gives a good response behavior when acetic acid is to be determined, while the same addition gives relatively small values for water vapor moisture

In another example, the addition of samarium results in a very high Y / resistance variation for dimethylformamide, while the effect is very low with moisture ₀

It was also found that the rare earths were also incorporated into the ferroelectric crystals as additives can be used if hydrogen sulfite is to be determined, which is present in the polar liquid vapor of crude oil »

In Fig. 2 is a modified embodiment of the invention shown, which consists of a suitable ferroelectric or ferrielectric substance, as described above, Has produced crystal. The area walls are again indicated schematically by reference numeral 32, and the positive and negative signs point to the oppositely polarized ones, through the area walls separate surfaces. The few areas shown schematically in this figure are only given as examples for the areas shown in plan view. to understand, which are generally about in a kind of "semi-random" form the entire crystal structure are distributed.

Similar- ^ lectroes may suitably be at opposite Sides of the crystal, as can be seen for one of the electrodes 34 from FIG. This generally denotes nothing of the reference chain 34 Electrode is a generally cylindrical means - piece on j that with a look! elongated, after

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is provided radially extending parts 38 on the outside ,. A suitable electrical conductor or connector 40 is connected to the electrode. A similar electrode structure is on the opposite side of the crystal intended.

This particular electrode configuration exhibits in proportion a large outer peripheral line to the electrode surface and proved to be more effective than a simple circular one Electrode as used in conjunction with Pig. 1 described v / urde.

Various other electrode configurations can also be used to be used with the aim of the outer peripheral line for a given electrical surface to be irex larger · It however, it is again emphasized that the free crystal surface should be large relative to the electrode surface, in particular

- re should be this ratio of free crystal area to

Electrode cloths should be at least as large as -the ratio- nisse C / C and gVG, which result from table I *

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They should be free of charge in general be ten times as large as the electrode area and in some cases 50 times as large or even larger »

In the example shown in FIG. 3, sin becomes the above Crystals similar to crystal 50 used, with this embodiment of the invention the "two with the crystal in contact electrodes together are arranged on an end face of the crystal. The first electrode has a central portion 52 aui, with a number elongated ropes 54 protruding outward in radial sighting are provided. With this -electrode is an electric Terminal 55 connected. The other electrode is Tse a generally circular part 58 air? marked in

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radial direction inwardly projecting elongated parts 60 is provided in the spaces between the elongated parts 54 of the other electrode come to stand. An electrical connector 64 is with the second Sieztrode connected.

It can be seen that with this arrangement there is a maximum outer circumferential line for each of the spatially separated Electrodes for the area in question is achieved.

In this case, too, the free crystal surface should be significantly larger than the electrode surface In roughly the same ratio as described above. In this example the free crystal face includes the visible one xeil of the Srlställofeerflache In FIg. 3 that is not of covered by the electrodes. In this embodiment, the free crystal face closes the opposite one The end face of the crystal is not included, since, according to the definition, the free surface area is only that crystal surface comprises, on which electrodes are arranged.

In the execution bell according to Pig. 4 1st one of the above Similar Eln-Krlstall-plate 70 is provided, on one surface of which an electrode 72 is attached, ■ The 3ils of a number of protruding parts of the wall 74 is provided. A similar electrode 76 is mounted on the opposite face of the crystal and points to the enlargement of the outline or "üafangsabmes" Solution for a pre-ordered slefetrodenilähe the same configuration on.

3) Two connections 82 run through a base plate 80 and 84 j those carried by one of the bottom plate Insulating body 86 are held. Bas insulation material of the Body 85 can be the same as that used in stainless steel floor panels Material similar. The connection terminals 82 and 84 are

The electrodes 12 and 76 are correspondingly connected by connecting parts 90 and 92, for example by silver paste, by welding or the like. Here, too, the relative sizes of the free crystal pool correspond to Ixxlu. CtSX * ijiSjv oj? Ou. € il j. .1.3. CnS \ x ^ Tl VOj? O3? \ VS.ixii u6ii / Λ37j. * _ *. *. üvo. "Iwovii"

The crystal of the determining device is moved by a hood 96j via the bottom plate is protected and has a large number of holes 98, so that a po- \ larer gelan- liquid vapor to the crystal surface

'gen can. It can be seen that many other types of

• Protective housings for holding and protecting the inven-

Appropriate assessment or proof before the direction

applies to / can ground »

3? Ig. 5 shows an Irish circuit which contains the determining device according to the invention. Capacitive measuring or determining devices can be used as the capacitor 100, which forms a branch of a balanced Wlieatstone bridge, from one of the inventive functions described above. T Iag BriiGirsiigleieliigs the variable capacitance 102 and the variable resistance as well as by a correct selection of the resistor 1C8 can be set. An alternating voltage from a source connected to the connection lenses 110 and 112 is the bridge to the connection point of the resistors U 04 and 108 and to the connection terminal 118, which is formed by the connection of the capacitive measuring device 10C and the capacitance 102 - It is known to those skilled in the art that

{the potential differences cise the connections 114 and

\ 116 when the bridge is broken

The AaascM.iiSsleiEnnsii 114, 116 and 118 of the bridge are sown

* 'einsi Sospara.tci · 120 connected, of a Different :!

J can develop more strongly, with the outcome of the

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is an electrical display instrument 122, for example a milliammeter or similar measuring device, connected "

If the measuring or, as a rule, condensate or 100 polar liquid vapors is exposed, the capacitance or resistance c j of both changes and brings the bridge out of equilibrium. As a result, the output of the eciaparator 120 is displayed by the display device
monitored, and the steam cone present in the devotion can be read τ.-earth. It can also be seen that a suitable recording biw. Storage device can be used in place of display device 122.

In Pig. 6 the Heß- or liachv / ei skond ensat or 130 in
its structural design, for example, one of the Pig execution forms according to the invention. 1 to 4 correspond. This capacitor is also in a
Yßieatstone's see bridge arrangement which has a variable capacitance 132, a variable resistance 134 and a resistance 136. In this embodiment of the device, the device for generating the alternating control voltage contains a small transistorized Colpit oscillator 150 which is connected to the Wheatstone bridge via a coupling capacitor 152. Me excitement
of the oscillator v / ird - as known - generated via an oscillator circuit and a corresponding feedback. The inductance and capacitance values of the oscillator are chosen so that a required alternating current frequency is generated and, if necessary, it can be provided with suitable amplifiers in order to obtain a suitable adjustable voltage so that the
Area configuration of the ferroelectric crystal element is not switched.

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The bridge balancing can be done by the variable capacity and the variable "resistor 134 and through correct Selection of the resistor 136 can be set.

The output of the Wheatstone · see bridge is with the input terminals 154 and 156 of a functional or arithmetic amplifier 160 connected. The amplifier corresponds to that commercially available type Amelco 809 C, which is integrated in Circuit is constructed and made by Amelco Semiconductor, Division of Teledyne Inc., 1300 Terra Bella Avenue, Mountain View, California. This well-known and widespread ie functional amplifier, the is formed in a small silicon chip 'is enclosed by a TO 5 package.

Between the output terminal 162 and the input terminal of the amplifier there is a negative feedback via a resistor I64. Between terminals 166 and 168 of the amplifier are used as compensation elements to avoid undesired oscillations of the amplifier a resistor 172 and a capacitor 174. Resistor 176 also simulates that of input terminal 156 Ground is connected, also part of the compensation network. Terminal 180 is positive Battery voltage, while the terminal 182 is supplied with a negative battery voltage.

If the bridge has been adjusted, I54 and are at the input 156 of the puncture amplifier no tension, and accordingly no output signal appears at the output terminal 162. If the determination device according to the invention or the capacitor 130 is exposed to polar liquid vapor, so the capacitance or the resistance or both change depending on the amount of polar Liquid vapor, and the bridge gets out of balance

Besientsprechsna changes the output signal of the puncture intensifier proportional to the amount of that deposited on the crystal surface of the training device 130 Steam.

The output cycle Hne 162 of the amplifier is across resistors 1S0 and 192 z? It a controllable silicon rectifier 194 connected, which has a load impedance 1So, which, shown schematically, is formed by a resistor in series with a positive voltage source. the controllable silicon rectifier is through a negative

§ Potential source 198 is pre-charged. The one at the exit point

162 of the amplifier potential can be adjusted by changing the y / resistor 190 in order to obtain a certain trigger voltage or a trigger voltage level from which the controllable silicon rectifier becomes conductive and a suitable control device, for example a Seiais, a motor or similar turns on in that the drive coil or a resistor of such a control device is used as the load impedance.

Accordingly, it is possible to set a certain threshold value or a starting point for controlling an air humidification or Adjust the dehumidification system so that suitable control devices for the humidity through the Circuit can be switched on or off. By Adjusting the level of the bias voltage can control the switching operation so that a desired level is achieved Humidity arises. Ss can be seen that instead of of the controlled silicon alignment a magnetic relay or a transistor switch and the like as well can be used.

The use of a puncture intensifier as described in Pig. 6 increases the sensitivity of the arrangement considerable, and there is a linear increase

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I relationship between the output variable of the ferro-

I equipped with an electric crystal

I tion and the output size of the puncture amplifier.

According to Pig. 7 are two electronic oscillators 200 and 202, which are surrounded by a sealed envelope, shown schematically by a dashed line 204 ' are provided.

I The oscillator 200 can be tuned and is

I mation to a predetermined frequency as a reference oscillator

I used tor. This oscillator contains a wide

I starting independent capacitor 208, which has a predetermined

I determined plague frequency. This could, if desired,

I can also be a crystal stabilized oscillator.

I The tuning of the second oscillator 202 is through the

I ferroelectric determination device according to the invention

I 210 determined that of the in Pig. 4 shown approximately

I corresponds to. The condenser 210 containing the condenser 210

I determining device according to the invention changes under

1 'the influence of polar liquid vapors, of course

I their capacity.

I The outputs of the two oscillators are on a mini

{ shear 212 switched so that an intermediate beat frequency

I quence arises which is caused by the

J direction 210 precipitated amount of polar liquid

I corresponds to the change in capacitance caused by steam. It is

! it goes without saying that suitable facilities are provided

are, so that an access of the surrounding air to the crystal of the determination device 210 is assured, se that the presence of polar fluid vapor is determined ν / can ground.

ö I 1

The original beat frequency of the circuit can be determined by prior frequency tuning of the oscillator 200 relative to the frequency of the oscillator 202, so that a desired measurement range for a certain range the occurring humidity can be adjusted. The output of the determination device can, as in Pig. 7 illustrates a digital one, if desired Output ^ be so that digital counters, oscillographic and other display devices operated can be. This allows the humidity data to be transmitted over a telephone line, as a Attenuation or fading of the signals does not affect their frequency.

From the above it follows that with the invention a new detection, measuring or determining device for polar Liquid vapor is present which is responsive to changes in the content of polar liquid vapor, such as about humidity and similar environmental parameters, ιιηα that the output signal or signals of the invention Circuits for displaying or measuring the vapors, for operating suitable recording and / or storage devices or can be used for control devices, so are any suitable devices desired © of the devices.

Claims (1)

Gases A-61
OLP 584- Protective violations 1. Device for detection, for determination "or for Measurement of polar liquids, characterized by a ferroelectric or ferrielectric crystal, to improve "or enlarge the occurring under the influence of polar liquid vapors Changes in its electrical properties are provided with one or more additives and at least has two separate electrodes that are generally in contact with the crystal » 2. Device according to claim 1, characterized in that that the crystal consists of a single crystal flake consists. 3. Device according to claim ί or 2, characterized in that that the crystal consists of bismuth titanate and the additive or additives contain tantalum. 4. Device according to at least one of the preceding claims, characterized in that the one or more additives Contains hafnium, chromium and / or niobium. 5. Device according to at least one of claims 1 to 3 » characterized in that the ferroelectric crystal Uodium potassium niobate, sodium niobate vanadate, lithium niobate and / or contains barium sodium niobate. 6. Device according v / enigstens one of the preceding claims, characterized in that the crystal over a period of generally from 5 to 10 minutes at a temperature range of about 400 to 500 ⁰ C wärmebe- egg acts, do so a greater sensitivity to achieve ^. 7c device according to at least one of the preceding claims, characterized in that the amount of the additive (s) is in the range from about 0.001 to 10 mol- ^. 8, device according to claim 1 or 2 or at least one of claims 5 to 7, characterized in that for Increasing the sensitivity of the capacitance changes gene of the crystal of the additive (s) strontium. " Contains lanthanum, zircon and / or chrome. 9. Apparatus according to claim 1 or 2 or at least one of claims 5 "to 7, characterized in that for Increasing the sensitivity of changes in resistance of the crystal of the additive (s) lanthanum, liioh, tantalum and / or contain colybdenum. 10. Apparatus according to claim 1 or 2, characterized net that the crystal can be used "at humid- ity provisions made of bismuth titanate "and the or the additives zirconium, hafnium, kiobium, tantalum and / or chromium contained and in terms of quantity in the range of about 0.05 his 3 mo1- $ lie4 11. The device according to at least one of claims 1 or 2, characterized in that the crystal, when used for the determination of acetic acid, contains additions of kangan and for the determination of dimethylformamide, additions of samarium. 12. The device according to claim 1 or 2, characterized in that the crystal is particularly suitable for determining polar liquid vapors from crude oils if it contains bismuth titanate and / or the additives contain one or more of the rare earths ~ 26 - 13. The device according to at least one of the preceding claims, characterized in that the free The crystal surface of the electrode-provided part of the crystal surface is much larger than that Electrode area * 14o device according to claim 13, characterized in that that the free crystal area is at least ten times larger than the electrode area. 15 · Device according to claims 13 or 14, characterized in that the ratio of free crystal surface to electrode surface is at least as large either as the ratio C / C or as the ratio G / G, where the variables C and G correspond to the value of Crystal capacity or the specific crystal resistance at 100 i ° air humidity, while the variables C and G correspond to the corresponding capacitance or specific ■ resistance value at approximately 0 <$> air humidity « 16 _e device according to at least one of the preceding claims, characterized in that the outer circumferential line of the electrodes is large relative to the surface thereof. 17o Apparatus according to "at least one of claims 1 to, or at least one of claims 7 to 16, characterized in that the electrodes are applied to the crystal at a ieisperatur of about 400 ⁰ C" 18 «device according to at least one of claims 2 to 17, characterized in that the electrodes on opposite sides End faces of the crystal plate are arranged. 19. The device according to at least one of the preceding claims, characterized in that at least one the electrode comprises a plurality of relatively narrow, elongated sections I to "at a given electrode \ a large surface contour or line TJmfangs / received - ¹ 20. Device according to at least one of claims 2 to 19 »J characterized in that two electrodes in common | are arranged on one side of the crystal, where ι each of the electrodes has a number of mutually separated, | having elongated interlocking subsections, the subsections of each electrode are spatially separated from those of the others and the electrodes have a large area for a given area Have a border line. β device according to at least one of claims 2 to 17, characterized in that the electrodes of the wafer angeord- net on opposite end surfaces, that the electrode Every a No. ahl l äng - borrowed trained subsections to the TSm- Jl * gIz1 \ z \ Xxx ^ o jl 3_xx3- S \ xS 336x u ^ xi x. ΐϊχ? ^ jLxxi? i £> ^^^ u6j16 ^ i _i_ ^ ä τ «ϊΓλ7 ^ λ"! γττ ^ area to increase, and that around the electrode provided crystal to avoid damage a protective cover is provided. 22ο Device according to claim 21, characterized in that the protective cover has a housing (96) which essentially surrounds the crystal and the electrodes attached to it, that the housing is provided with holes (98) so that polar liquids fight ± a intimate To be able to come into contact with the rules of determination "