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Building on almost 35 years experience with alcohol fuel cell sensors
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The scope of our registration is:
The design and manufacture of chemical sensors. The manufacture of reference standards. The supply of chemical sensors, catalysts, fuel cells, reference standards and associated components.
Our certificate of registration can be found here.
In order to do this we will:
1. How does it work?
Dart chemical sensors operate by means of the fuel cell principle. A fuel cell is a chemical battery to which the fuel and oxidant are continuously supplied, so in principle it is everlasting.
We should explain here what a �battery� is (strictly speaking, an electrochemical cell). Many chemical reactions consist of a transfer of electrons from one reactant to another. To take a simple example, the reaction of zinc with manganese dioxide. If heated together, the following reaction can take place:
Zn + MnO2 = ZnO + MnO
Underlying this change, is an oxidation (loss of two electrons) from each zinc atom, and a reduction (gain of two electrons) by the manganese atom.
If instead of mixing the two ingredients together, we keep them separate and force the electrons to make their way along a wire to reach their destination, we have the basis of the familiar AA, AAA, PP3 batteries.
To complete the electrical circuit, the zinc and manganese dioxide �electrodes� also need a connecting liquid pathway, the �electrolyte�, in the above example commonly an alkali (so the battery is known as alkaline manganese).
2. What is it made of?
The electrodes are of platinum, high quality, high surface area, made by our own processing method developed over 25 years to achieve high performance, calibration stability and long life; the electrolyte is an acid. Contact wires preferably are platinum too, not too thin (fragile), not too thick (expensive).
3. How to operate the sensor?
Breath alcohol sensors are almost always operated with a snap sample (see section 8 below) taken near the end of an exhalation, and signal processing may be classified according to whether it is by peak voltage or a current integration method. The course of breath expiration is detected with the aid of a pressure switch, a heated thermistor, or a microphone.
4. What is peak voltage measurement?
Originally, breath alcohol sensors were operated only in �peak mode�, that is to say the sensor was connected to a shunt resistor, initially of 1000 ohms, the peak voltage response across the resistor being measured. Sensors then were slow in operation, response times of around 40 seconds were commonplace, and clearing time was up to five minutes (today, we can obtain peak times of as little as 200 mS and clearing times well below 5 seconds). Peak measurement is still used for some applications as it is less affected by adverse conditions (see 7 below) but has two disadvantages compared with integration and is avoided where possible:
Repeatability improves with higher load resistances, but the response time is extended, and so a compromise is sought which is generally between about 220R and 390R. Once the peak value is passed, it is usual to short the sensor to speed up clearing. A JFET is normally used for this purpose.
5. What is the current integration method?
The development of much faster sensors alongside cheap microprocessors has enabled more complex algorithms to be used in signal processing. A rigorous treatment would be full integration of the response curve, but this has not been found necessary for adequate accuracy, repeatability and calibration stability.
The sensor must either have a low load resistor value (typically 10 ohms or less), if a V/V amplifier configuration used, or (as we favour) an I/V (transimpedance) configuration which gives effectively a zero resistance. Either provides fast response and clearing times. Integration of the response down to 10% of peak value or less is adequate to give very stable short and long term calibration stability. But your electronics must be low-noise (more on this in 16 below).
6. What is the lifetime of the sensors?
There is no simple answer to this. Old fuel cells never die, they only fade away. In theory they are everlasting (short of gross contamination) as nothing is consumed during use (although we are aware of competitor products which generally last much less than a year). In practice, they get slower and slower owing to some combination of poisoning and slow surface area loss of the platinum catalyst. Sensor size is not an important factor.
For unheated sensors, service lifetimes of ten years are known, but the answer really is �until, in your opinion, they get too slow to be of practical use, or can no longer be calibrated� (but even then a component change to raise the gain may bring them back into service). Five years is typical. And you cannot really over-use them, if fact they seem to last longer when well-used than when hardly used at all.
When sensors are permanently heated, outputs may drop more with time. For example, in an evidential unit introduced in 1998 which has sensors maintained at 38C, outputs are sustained by increasing amplifier gain as required. In 2005-2007 a rolling programme of replacements was carried out as a precautionary measure. Many of the sensors replaced were those originally installed in 1998. They had slowed somewhat in early years, after which little further change was observed.
Prolonged exposure to very low humidity leads to short sensor life (more below, Q 13).
7. What are the essential differences between the five sensor �types�?
Working in reverse order:
Type 5 is the standard formulation used universally since about 1982. We consider it useful in three instances:
Type 4 has been used by us since about 1993. It gives a very fast response and clearing time, and has very good low temperature properties, but is unsuitable for applications where the sensor is likely to see frequent or prolonged exposures above 50C. Integration is best.
Types 1, 2 and 3 are various formulations introduced in about 2004, principally for interlock products where resistance to short term exposures at high temperatures (up to 85C) is essential. There is as yet no consensus on which is the best. Peak measurement gives best results.
8. What sample volume should be used?
The original 32mm diameter size used a sample volume of about 1.2 cm3. All other things being equal, and with a sample pump capable of precise delivery, the sensor area can be reduced in proportion to the sample volume. So a 16mm diameter disc works just as effectively with a sample volume of around 0.3cm3 , the 11 mm with 0.25cm3 . In practice, a precise sample volume in the range 0.25 cm3 to 0.50 cm3 works well for these sizes. The smaller the better, as long as the volume is precise and the electronics can cope with the lower signals.
Recent work suggests that the best way to operate the pump is to take the sample, hold for about 200 mS, then reset. Alcohol vapour is taken up very rapidly in to the sensor wafer. Drawing in first, then blowing out, is the preferred method.
We are often asked where to source the pump. Most manufacturers make their own with a bought-in solenoid and their own design of diaphragm parts. Sensatronic manufacture a very high quality sample pump available in a variety of sample volumes.
http://www.sensatronic.com/de/
9. How often to calibrate?
In units using the integration method, the calibration should be very stable. Calibration checks are carried out at 6 monthly intervals in the case of the UK police evidential equipment, but that is a statutory requirement, and few would need a recalibration at this interval. There are instances known of hand-held units containing our sensors which have held calibration (35 +/- 2) for up to six years. So the best advice is to check as often as you think necessary.
Here are some guidelines on performance expectations.
A sensor made with freshly-prepared components displays hyperactivity. Peaks will drop and response time slow a bit in the first months, then they steady up. Calibration may fall initially (peak mode is more affected).
10. How to calibrate?
There are two commonly used methods, a �wet� gas and a �dry� gas.
A wet gas uses a liquid calibration standard in a breath alcohol �simulator�. The most popular simulator now is probably the Guth made by Guth Labs in the USA. We supply certified liquid standards, mostly for the UK market, as export is expensive owing to the large weight of the glass bottle and the water content. They are used in some countries as a traceable reference for locally made standards. Our Dry Alcohol Standard (DAS) is a way of reducing weight, the end user simply adding water to obtain the liquid standard, but please note, as they are individually made they cannot be certified.
A dry gas uses a compressed alcohol/air mixture in a gas cylinder. Note that the fuel cell sensor reads dry and wet gases differently, the difference typically being about 6% higher for the wet, and so a correction � the �wet/dry factor� - must be made to adjust the dry result up. Also with a dry gas, a correction must be made for variation from standard barometric pressure as the dry gas will expand more into a low pressure atmosphere than a high pressure and so have a lower concentration.
The output is linear so single point calibration is normal, the chosen value usually being the legal limit in the jurisdiction of the purchaser. For additional accuracy (for police use) calibration at three temperatures is usual�see 12 below.
11. 2300, 2100, what is that all about?
Body alcohol levels were originally measured from blood samples. When breath analysis began, it was necessary to find a relationship between blood and breath.
A retired former forensic scientist who had worked for the UK service told me of a survey carried out on a fairly large random sample of people, and the relationship
alcohol concentration in blood / alcohol concentration in breath
was found to vary between 1,600 and 2,900. Choosing a fixed point is therefore somewhat arbitrary, and the two ratios most used are around the median value, 2300/1 in the UK and 2100/1 in the USA.
It is important to realise that the breath values are absolute. In the UK the limit value is 35 microgrammes of alcohol in 100 cm3 breath, which is 191.4 ppm ethanol, and this equates to 80mg/100 ml blood at 2300/1. In the US, an 80mg blood value is held to equate to 38 microgrammes.
12. What effect does temperature have?
First, the speed of response increases with temperature.
Secondly, there is a temperature coefficient to the response. The measured output (peak or integrated) rises with increase in temperature until somewhere in the region 20C to 40C, then gently falls. We are often asked to provide temperature coefficient data for sensors, but they depend on the details of the installation and anyway vary a little from sensor to sensor, so for most accurate set-up (for police use at least) you should calibrate each unit individually at least at three temperatures � 5C, 20C, 40C are commonly chosen � generating a compensation algorithm.
Finally, it may shorten sensor life to some extent, particularly if accompanied by very low humidity. Formulations designed for interlock use have the highest resistance to temperature.
13. What effect does humidity have?
Electrochemical sensors of most types usually have a limited recommended humidity range for operation, for example 30% to 95%. At or near 100% they are liable to absorb moisture and flood.
At very low humidities the electrolyte volume will shrink enough to produce low results. This first became apparent many years ago when screeners put into Arizona were found to have a very short sensor life. There is however another more subtle situations. When the temperature falls below zero, the water content of the atmosphere drops sharply. The worst situation is where the outside temperature is low and the sensors/units are stored unprotected in a heated building, where I guess the relative humidity is close to zero. Please note that prolonged exposure to such low humidity invalidates the warranty.
In some instances, sensors appear to recover when exposed to high humidity again, but data are as yet incomplete and inconsistent.
Meanwhile, as for fixes where continuous low humidity might be a problem, either store sensors/units in airtight containers or in a medium/high humidity environment; or design units so that the sensor is sealed off when not in use. It seems that it is storage which is critical, if they are being used frequently with wet gas/breath the problem does not seem so critical.
14. Are the sensors sensitive to substances other than ethanol?
Yes, but these �interfering� substances are unlikely, except in very extreme circumstances, to cause a problem. One of the reasons why the fuel cell sensor is ousting the semiconductor type is its greater specificity � it is, for example, not sensitive to acetone, which can occur in substantial qualities in the breath of diabetics.
The fuel cell sensor routinely passes the specificity requirement for breath alcohol equipment approvals - for example, all the tests required by the authorities in USA and the UK for evidential use. But to give actual examples:
It has no sensitivity to the following substances: acetone and other ketones; toluene, benzene and other aromatic hydrocarbons; ethyl acetate and similar esters; methane, ethane and other saturated hydrocarbons; carbon dioxide; water vapour (brief transients may occur).
There is sensitivity to the following within the limits specified by the UK Home Office: methyl alcohol, isopropanol, carbon monoxide, diethyl ether.
It is also sensitive in varying degrees to: hydrogen sulphide, sulphur dioxide, aldehydes including formaldehyde, phenol, hydrogen, alkenes. NOx and ozone give a negative response.
15. Do I need to heat it?
Sensors are heated in the following applications.
For battery powered units, heating is unusual owing to the power drain.
For -20C operation it is usual to heat the sensor. It is very slow at that temperature and gives about 10% of the ambient value. Also there are likely to be problems with condensation from breath, which leads to unreliable results. So it is good to get some heat into the sensor and also into the breath pathway to prevent condensation. Worth mentioning at this point, in your design, keep the sample pathway from mouthpiece to sensor as short as possible, or condensation can occur there leading to low results.
The type 4 formulation is better at low temperatures, but is not suited to a high temperature exposure. If you want an interlock sensor to come to working temperature quickly, it can be operated at just 20C, or anything down to 5C, or even lower. So the heater device can be set to operate when the temperature falls below the temperature of your choice. Then you may need to use some temperature compensation for the expected upper temperature range.
The usual way to heat the sensor is with a heated metal (usually aluminium) block. The sensor is attached to the block. The heat is supplied by a power transistor and controlled by means of a thermistor next to it � it needs to be as close as possible to avoid hysteresis swings of temperature. Watch out for the thermal offset which occurs during the heating-up stage.
16. Some of your competitors use a pair of single sided wafers. Why? What difference does that make?
Why? Because they haven�t yet figured out how to double coat the substrate.
When the electrode coatings are on separate wafers, there is an imperfect electrical connection between the two. This gives rise to an internal resistance which can vary from one sensor to another, and it can change from time to time in each sensor as the electrolyte volume varies with changes in temperature and humidity. This means that there can be a wide difference in properties between sensors in a batch, and variations in properties within a sensor during its lifetime.
With our double coating, and patented biporous components, the geometry of the sensor electrodes is fixed, and the electrolyte variations are largely confined to the reservoir wafer, an uncoated component, which gives good batch consistency and long term calibration stability.
17. Right, how do I get started?
18. Any traps to watch out for?
Results not as good as you expected?
Is your baseline steady and low in noise (see 16 below)?
Are you getting a build-up of condensation near the sensor inlet (keep gas pathway short and heat if necessary to 35C minimum).
Noise spike from solenoid operation?
Did you use a dual rail, low noise amplifier (see 16)?
19. The sensor was OK when new, but now is not so good.
We have seen a few examples of this. Don't automatically blame the sensor, it may be a matter of signal/noise. When new, the sensor (particularly type 4) has a very sharp spike response followed by a quick clean-up, and even quite indifferent electronics will not hamper accurate determination of the integration cut-off point. But the fuel cell profile changes shape with age, the sharp spike drops away and the tail grows longer. If the output is noisy, the software grabs at the first dip to find the cut-off point, and takes it too early. It will be more of a problem at low alcohol levels, results will be low. Linearity is therefore affected.
Here are five remedies you can explore.
Incidentally, you can anticipate the ageing of the peak spike by allowing the sensor output to hit the rail on high values when new: integration carries on just the same (but the cut-off point is slightly altered).
20. What is the lowest ethanol detection limit?
Under practical conditions the sensor has no diffficulty reading down to 5 mg/100 ml, 0.005 BAC, which is a commonly chosen cut-off point.
Under ideal conditions less than 1 ppm is possible, but the humidity of human breath and possible low level CO in smokers give transients which become significant at low levels.
21. And finally....
Accurate results depend on a combination of five ingredients: a good sensor, a precise and reliable sampling system, quality electronics, sound software and correct calibration (to which we can add, realistic expectations on the part of the user�do not expect evidential quality from a $30 breathalyser). So when something goes wrong, don�t automatically blame the sensor. Usually (but not always!) the fault lies somewhere else.
Remember, we are here to help you.
We will then contact you to advise of a course of action.
Remember that the more detail you put into the fault desctription, the easier it will be for our engineers to reproduce the alleged fault.
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Returned items confirmed as faulty will be replaced by an identical product (or a product of similar specification), sent for repair or credited depending on the age, condition and status of the product and the availability of an appropriate replacement.
Dart Sensors diffusion sensor products are best operated in conjunction with a high gain transimpedance (current to voltage) op-amp circuit. Gain resistors of the order of 1M are typical. A high gain, low input current offset op amp is essential.
The sensor will pick up an offset if left unpowered. They are shorted out for delivery. They should have a means of keeping shorted in operation. A shunt resistor of about 470 ohms will suffice, but a jfet is a more elegant solution.
Temperature compensationIf you want to achieve a high degree of accuracy, then you should apply a temperature-dependent compensation. Temperature/response curves will follow shortly.
Diagrams of sensor housings can be found on the datasheets page.
Further informationDart Sensors gives full technical support to users of its products. If you have any queries which have not been addressed above please contact us at customer.service@dart-sensors.com
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