JPH06117976A - Simple method and device for measuring environmental atmosphere - Google Patents

Abstract

PURPOSE:To obtain a method and device for measuring the average concentration of a specific gas in a certain environment for a long time simply and accurately using an inexpensive and compact device. CONSTITUTION:After a metal, ceramic, or a metal salt is left in an environmental atmosphere for a specific period, an adsorbed gas is analyzed. Especially, a porous metal or ceramics (transition metal oxide), a porous ceramic (rare earth element oxide), and a specific chloride such as copper chloride and silver chloride are superb in selective adsorption property for NOx, CO2, and SO2, respectively. A test kit for housing these test pieces in a case, or a protection case for test kit for putting the test kit into practical applications, an umbrella, and a reinforced air supply device are also disclosed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a simple environmental atmosphere measuring method and device, and more particularly, to a simple test piece which is left in the measuring environment, collected for a predetermined period of time, and then measured to measure the test gas. The present invention relates to a simple environmental atmosphere measuring method capable of knowing the atmosphere, a measurement kit therefor, a test piece protection case, and the like.

[0002]

2. Description of the Related Art In recent years, NO _x , CO ₂ or SO ₂ existing in the atmosphere has become a problem as an environmental problem. N
O _x is caused by exhaust gas from automobiles and factories, and the concentration of NO ₂ and NO is several ppb in the natural world, while it reaches a maximum of 50 ppb in big cities, which is a big social problem. The same applies to CO ₂ . Furthermore, the problem of acid rain is also serious, and it is considered that air pollution due to SO ₂ gas contained in the combustion gas of a factory is one of the major causes.

In recent years, electronic devices such as computers, for example, personal computers, word processors, facsimiles, telephones, notebook type personal computers, etc., are becoming smaller and lighter. These small electronic devices have a problem of corrosion damage. Conventional large-scale computers were installed in fully air-conditioned environments, so there were almost no cases of corrosion problems, but small-scale computers were used in all environments, and H ₂ S, Cl-based, humidity In addition to the above, in particular, there is a concern that troubles due to NO _x , SO _{2 and the} like will occur.

The present invention simply collects these gases,
It provides a way to analyze and monitor. Present
Currently NO_xIs a costly and large
There is a method of using a mold type automatic measuring device. This is Salz
Mann's reagent (phosphoric acid, sulfanilic acid, N1 naphthyl ethyl
Liquid in which diamine hydrochloride is dissolved in distilled water)
NO into the body _xPour a certain amount of air containing
Mu. This reagent and NO_xWhen a chemical reaction occurs, it turns pink
Changes to. This reagent is NO_xThe higher the concentration of
The black color becomes darker. Then shine a light on it,
Measure the thickness of the color-developing solution based on the size of the transmittance.

However, in this method, NO is generated at any place.
There are many drawbacks, such as the inability to measure _x and the need to analyze a huge amount of data in order to obtain a long-term average concentration because the collection period is primary (short period). Not something you can do. As a method for monitoring CO ₂ , there is a method using an expensive and large automatic measuring device or a semiconductor sensor. Since these methods cannot be measured anywhere, and the collection period is temporary (short period),
There is a drawback that a huge amount of data must be analyzed in order to know the long-term average concentration. In addition, a non-dispersive infrared spectrometer (NDIR) and a gas chromatograph (GC) are widely used for measuring CO ₂ gas, and the gas itself is introduced into the interior, and relative quantification can be performed from the absorptance obtained from the absorbance. Done. These methods are limited in places where they can be used, and in cities, there is no particular problem with equipment transportation, power connection, etc.
It is often difficult to operate such equipment in mountainous areas, forest areas and jungles.

[0006] As a method for measuring harmful gas containing SO ₂ gas, an absorbing solution is put in a collection bottle, which is then capped with a bubbler lid,
Directing ambient air into the absorption liquid by subtracting the air trapped within the bottle collecting pump, SO ₂ gas collecting method defined in JIS K-0103 to trap SO ₂ gas in the air in the absorption liquid A method is known in which the absorption liquid is chemically analyzed and then the result is converted into a concentration. With this method, only sulfur oxides can be collected and accurate values can be obtained, but in order to always operate the power supply for the pump and the collection device normally, it is necessary to have a person who has knowledge of the entire device, so sampling The place and time are limited.

[0007] Also, the potassium carbonate aqueous solution is soaked in the wind
Leave the dried filter paper in the environment for SO ₂Collect the gas,
There are known methods for chemical analysis of these and converting the results into concentrations.
There is. In this standing-type alkaline filter paper method, the collection work is
It's easy just to put the paper on the spot, but H₂S is SO
₃Because it is collected in the form of₂And H₂The distinction of S
There is an essential drawback that cannot be done.

Therefore, it is inexpensive, compact, and NO._x, CO
₂, SO₂ The gas such as
A method of easily monitoring the degree is desired. Similar to this
Applicant (Fujitsu Limited)
According to Japanese Patent Laid-Open No. 63-305232,
Developed and disclosed a method to monitor corrosive gas using a piece
Has been done. However, with this method, NO_x, C
O ₂Is difficult to collect and the accuracy is low.₂About
Is H₂Since it is difficult to distinguish it from S, the accuracy is poor.
There was a drawback.

Further, it is desirable that when the test piece as described above is left in various measurement environments, the handling property is improved and the cause of disturbing the measurement conditions can be eliminated.

[0010]

Therefore, the present invention is inexpensive, compact, and NO _x , C in an environment atmosphere.
It is an object of the present invention to provide a method for easily and accurately monitoring the average concentration of O ₂ and SO ₂ gas for a long period of time and a means therefor.

[0011]

The present invention achieves the above objects.
Broadly, to make, metal or ceramics or metal
Place the salt test piece in the environment where the measurement is to be performed
After that, the NO adsorbed on the test piece_x, CO₂Or SO₂
NO in the ambient atmosphere_x, CO₂ Or SO
₂To provide a method for measuring the environment characterized by
It In the present invention, "adsorption" is not limited to physical adsorption,
Includes chemisorption such as when collected by chemical reaction
The meaning should be understood.

Specifically, for NO _x , a porous metal or ceramic test piece or a test piece in which fine metal or ceramic powder is carried on an integral metal or ceramic piece is used. More specifically, the porous or fine-grained metal is any one of copper, silver, platinum, rhodium, ruthenium, palladium, iridium and nickel, and the porous or fine-grained ceramic is SiO ₂ -Al.
₂ O ₃ , YBa ₂ Cu ₃ O _x , CrO ₂ , Cr ₂ O ₃ ,
Fe ₂ O ₃ , Co ₂ O ₃ , SnO ₂ , CoAl ₂ O ₄ ,
It is preferably any one of CuO, Al ₂ O ₃ and MgO (generally a transition metal oxide in general). Further, the test piece may be filled with voids of a porous metal or ceramic piece with triethanolamine having an action of absorbing NO _x .

For CO ₂ , porous rare earth metal oxides such as La ₂ O ₃ , Ce ₂ O ₃ , Pr ₂ O ₃ and N are used.
d ₂ O ₃ , Pm ₂ O ₃ , Sm ₂ O ₃ , Eu ₂ O ₂ , Gd
₂ O ₃ , Tb ₂ O ₃ , Tb ₃ O ₇ , Dy ₂ O ₃ , Ho _{2
O 3, Er 2 O 3,} Tm 2 O 3, Yb 2 O 3, Lu 2 O
_Use test pieces such as ₃ . Further, for SO ₂ , a metal oxide having a free generation energy of chloride> sulfate, for example, copper chloride or silver chloride is used.

Even if two or more test pieces are used at the same time for monitoring, a metal piece (copper, copper, etc.) for corrosive gas monitoring as disclosed in the above-mentioned Japanese Patent Laid-Open No. 63-305232 is used.
(Silver, aluminum, iron, 52 alloy, or part of it)
Of course, it may be used together with other test pieces (for example, inorganic substances such as platinum, gold, and refractory metals, and organic substances may be used).

Further, according to the present invention, N in an ambient atmosphere is
An environment characterized by comprising a metal or ceramics or metal salt test piece for selectively adsorbing O _x , CO ₂ or SO ₂ and a case for leaving the test piece in an environment atmosphere in which measurement is to be performed NO _x , CO ₂ or SO in the atmosphere
A measurement kit for assaying ₂ is provided. The test piece of this measurement kit includes NO _x , CO ₂ or S as described above.
Test piece for monitoring O ₂ and the above-mentioned JP-A-63-30
The metal pieces and the like disclosed in Japanese Patent No. 5232 (which may be an organic substance) can be used in an appropriate combination.

Further, according to the present invention, a substrate carrying a test piece made of a metal or a ceramic or a metal salt for assaying an environmental atmosphere, which is preferably used for the above-mentioned measurement kit, and the test are provided. A cover mounted on the base so as to cover the strip, the cover or the portion of the base covering the main surface of the test piece being transparent, the main surface of the test piece being visible from the outside, and There is provided a test piece protection case for environmental research, which has an atmosphere gas inlet / outlet provided at a position other than a portion covering the main surface of the test piece.

This test piece protection case for environmental investigation is NO
It is not limited to the case including a test piece for monitoring _x , CO ₂ or SO ₂ , and is generally useful as a protective case for a test piece for environmental investigation. In a preferred embodiment, the test piece is placed on the base so that the main surface of the test piece is parallel to the bottom surface of the base, a transparent resin cover is attached to the base so as to cover the main surface of the test piece, and the atmosphere gas inlet / outlet is tested. The test piece shall be provided on both sides of the main surface of the test piece so that the air flows parallel to the main surface of the test piece, and has a collar for promoting the inflow of the air into the atmosphere gas inlet / outlet. Some include a further umbrella, and some further include a means for forcibly feeding atmospheric gas from the ambient atmosphere to the main surface of the test piece. It is desirable that the umbrella and the feeding means be configured as a device that can be used by mounting the above basic protective case as it is. A fan is simple as the atmosphere gas supply means, and if the atmosphere gas supply means is driven by a solar cell, the power transmission means can be omitted, which is particularly advantageous in remote areas.

Thus, according to the present invention, the sample fixing portion for accommodating the protective case for the environmental atmosphere gas measuring test piece, and the sample fixing portion are covered to protect the test piece from rain, snow and the like. An umbrella for a test piece protection case is provided, which comprises an umbrella portion and has an air inlet / outlet for a test piece of a test piece protection case housed in a sample fixing portion, and in a preferred embodiment, the umbrella portion has a conical shape. It is composed of a planar plate-like object, and the sample fixing part is composed of a cylindrical part for accommodating a sample formed from the plate-like part and a plurality of arms extending from the top of the conical part, and the sample fixing part is formed by the arm part. Some have a structure attached to the umbrella.

Further, it has an air inlet and an air outlet, and has a sample accommodation section and a fan for accommodating a protective case of a test piece for measuring ambient atmosphere gas in a communication space extending from the air inlet to the air outlet. Also provided is a forced air blower for a test piece protective case, which is capable of forming an air flow from an air inlet to an air outlet by this fan, in particular, the fan is driven by a battery (dry cell, solar cell, etc.). Is preferred.

[0020]

EXAMPLES Monitor of NO _x FIG. 1 (A) shows a principle explanatory diagram of the present invention in relation to measurement of NO _x . In the present invention, the porous metal or ceramic test piece 1 capable of adsorbing nitrogen oxides is placed in an environment for measurement for a predetermined period of time, and nitrogen oxides are formed on the surface of the metal or ceramic particles 2 inside the porous structure of the test piece 1. 3 is adsorbed and collected, and the amount of the adsorbed nitrogen is quantitatively analyzed by, for example, fluorescent X-ray analysis or the like to collect nitrogen oxides in a certain environment.
Perform an analysis. It is considered that the nitrogen oxide may be simply adsorbed to the test piece or may be fixed by reacting with the metal or the like of the test piece, but either may be used for the present invention. The environmental nitrogen oxide atmosphere can be determined based on the results of the analysis.

Incidentally, the quantitative analysis of the amount of nitrogen and the like can be carried out by using an X-ray photometric spectroscope (XPS), which is shown in FIG. 1 (B). FIG. 2 shows an example of a device for placing a test piece in the environment. An appropriate number of test pieces 8 are accommodated in the transparent container 7, and an opening 9 is provided on the side surface of the transparent container 7 for communicating the outside and the inside. One of the test pieces 8 is the nitrogen oxide test piece of the present invention, and the other test pieces are, for example, copper,
A piece of metal such as silver or aluminum that is used to inspect various corrosive substances in the environment (eg, hydrogen sulfide, sodium chloride, moisture, etc.). This container will be described in detail later.

Since nitrogen oxides are relatively poor in reactivity, even simple metal or ceramic pieces are easily scattered even if they are adsorbed on the surface, and they are not adsorbed enough to measure nitrogen oxides in the environment. . However, we have
When the test piece was made porous to adsorb nitrogen oxides, it was found that nitrogen oxides in the environment were adsorbed with sufficient efficiency for assaying.

As the material of the test piece capable of adsorbing nitrogen oxide used in the present invention, copper,
Preferred ceramic materials such as silver, gold, platinum, rhodium, ruthenium, palladium, iridium, and nickel are SiO ₂ —Al ₂ O ₃ (especially SiO ₂ —xAl ₂ O _3).
(X ≦ 0.15)), YBa ₂ Cu ₃ O _x , CrO ₂ ,
Cr ₂ O ₃ , Fe ₂ O ₃ , Co ₂ O ₃ , SnO ₂ , Co
Examples thereof include Al ₂ O ₄ , CuO, Al ₂ O ₃ and MgO.

These materials are excellent in the ability to adsorb and fix nitrogen oxides, but it is particularly preferable to make the oxide ceramics in an oxygen-deficient state because the ability to fix nitrogen oxides is improved. The oxide ceramic in the oxygen-deficient state may be produced by, for example, heat treating the oxide ceramic in a reducing atmosphere. The porous test piece may be prepared by simply molding (for example, pressing) a metal or ceramic powder, or may be fired at a relatively low temperature and sintered to be porous (low density).

Fine ceramic or metal powder may be present in the voids of the porous metal or ceramic piece. For example, by sprinkling fine ceramic powder on the surface of the metal powder and molding or firing this metal powder to form a porous test piece, it is possible to obtain finer particles than when molding or firing a single ceramic particle. A test piece containing ceramic and having an increased specific surface area can be obtained. Further, fine ceramic or metal powder may be carried on an integral metal or ceramic piece. For example, an integral metal piece can be machined from a metal plate to provide irregularities or to form a bottomed hole or a through hole to facilitate carrying of the ceramic powder. Alternatively, after producing a porous sintered metal or ceramic piece, the porous sintered piece may be filled with fine ceramic or metal powder by means such as impregnation.

Also, holes in the porous metal or ceramic piece
Triethanolamine (C₂H _FourOH)₃Fill with N
Even so, triethanolamine absorbs nitrogen oxides.
Since it is stored, it can be used in the same way. Metal making test specimen
Or, the ceramic powder includes, but is not limited to, particle size
It is preferable to use a powder having a particle size of 200 μm or less. 200 μ
If it is larger than m, necking during low temperature sintering hardly occurs.
This is because the strength cannot be obtained. Also smaller than 30 μm
If sintering is performed at a low temperature, necking easily occurs and the density is
Since it may rise and the surface area may decrease,
In particular, a particle size within the range of 30 to 200 μm is preferable. However,
If the density of the porous part can be reduced, particles smaller than 30 μm
The diameter may be different, and the smaller the particle size, the larger the specific surface area.
It is preferable because Coated with the above fine ceramic powder,
In the case of the mode of filling or supporting, very fine,
For example, a powder of 0.05 to 5 μm can be used.

The density of the test piece is 7 g / cm for porous metal.
³ or less, preferably 2 g / cm ³ or less for porous ceramics. In the case of the metal-ceramic composite test piece, the density depends on the composite ratio. By such a density, big surface area, i.e., NO _x is obtained adsorption easily specimen, because it is possible to quantitatively analyze with sufficient sensitivity.

Since the amount of nitrogen oxides adsorbed on this test piece is a function of the NO _x gas concentration and time, it is recovered after being left for a long time (for example, one month) and various analyzers are used. The average concentration of the NO _x gas concentration at that location can be easily detected by performing the analysis. That is, according to the present invention, it is possible to easily achieve a monitoring method that is inexpensive, small-sized, and simply measures the long-term average NO _x concentration at a certain place.

[0029] For the monitor of the monitor CO ₂ in CO ₂ is the same as the monitoring of the NO _x, however, may be used those excellent in the ability to selectively adsorb CO ₂ as test pieces. Specifically, ceramics are made porous and have a low density, and in particular, La ₂ O ₃ ,
Ce ₂ O ₃ , Pr ₂ O ₃ , Nd ₂ O ₃ , Pm ₂ O ₃ , S
m ₂ O ₃ , Eu ₂ O ₃ , Gd ₂ O ₃ , Tb ₂ O ₃ , Tb
₄ O ₇ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm ₂
It has been found that the use of rare earth oxides such as O ₃ , Yb ₂ O ₃ and Lu ₂ O ₃ enables adsorption with sufficient efficiency for assaying CO ₂ in the environment.

The porosity, pore size, particle size and the like of the porous test piece can be the same as those of the NO _x monitor test piece. In the quantification of CO _{2 by} an X-ray photoelectron spectrometer (XPS), the peaks of C existing at 285 to 290 eV are separated and the area ratio of C peaks corresponding to CO ₂ is obtained. Further, a quantitative value of C is obtained from the area of the entire C peak and the peak areas of all the detected elements. The product of the quantitative value of C and the area ratio corresponds to the quantitative determination of CO ₂ .

SO ₂ monitor The SO ₂ monitor is basically the same as the NO _x monitor, except that a test piece that selectively adsorbs and reacts with SO ₂ is used. In particular, the selectivity of SO ₂ is important when it is desired to distinguish between H ₂ S and SO ₂ . For this reason, the following study was conducted.

In the natural state, the lower the standard energy of formation, the more stable the substance is. Then, focusing on this principle, we searched for a stable sulfate. As a result, the following sulfates are considered to be stable. Sulfate standard energy of formation (ΔGf ° / kj mol ⁻¹ ) Ag ₂ SO ₃ −411.3 Ag ₂ SO ₄ −618.48 Cu SO ₄ −660.90 Next, if a compound with a higher standard energy of formation than the above sulfate is selected, good. However, depending on the compound,
There is a possibility of reacting with H ₂ S, NO ₂ and O ₂ in the environment to form sulfides, nitrates and oxides. This becomes a factor that hinders the collection of SO ₂ only. Therefore, the standard energies of formation of sulfides, nitrates and oxides of copper and silver were investigated. The results are shown below.

Standard formation energy of sulfide / oxide / nitrate (ΔGf ° / kjmol ⁻¹ ) Ag ₂ S − 39.46 Ag ₂ O − 11.21 Ag ₂ NO ₃ − 33.47 Cu ₂ S − 86.20 CuO − 128.12 Cu (NO ₃ ) ₂ -102.9 Consequently, standard formation energy of sulfide, oxide and it can be seen that a lower than nitrate may be selected to compound. Therefore, the following compounds were selected as compounds having a standard energy of formation higher than that of sulfates and lower than that of sulfides, nitrates and oxides.

Compound standard energy of formation (ΔGf ° / kjmol ⁻¹ ) AgCl −109.80 CuCl −120.9 Incidentally, it is needless to say that these sulfates and compounds are a part, and can be applied to all if the conditions described so far are met. .

As the test pieces using copper chloride CuCl and silver chloride AgCl, those in which CuCl and AgCl layers are formed by chlorinating the surface of a metal plate of copper and silver in a chlorine atmosphere are easy to handle, CuCl and AgCl. It is preferable in terms of the adhesion of the layer.

Measurement kit Since the test piece excellent in selective adsorption of NO _x , CO ₂ and SO ₂ as described above is housed in a case and left to stand in an environmental atmosphere to be measured, these test pieces are used. The case where one or more of the test pieces is housed in the case is NO _x , CO ₂ , S in the environment.
It is useful as a measurement kit for assaying O ₂ .

As described above, this measurement kit contains N
In addition to the test pieces for certifying O _x , CO ₂ and SO ₂ ,
It can be used in combination with the metal test piece disclosed in 63-305232 and other test pieces (which may be organic substances).

Protective Case (1) For the purpose of the present invention, the case of the above-mentioned measurement kit may be any one as long as it accommodates the test piece and facilitates leaving the test piece in the measurement environment. Particularly, when a test piece of a corrosive gas is included, the corrosive gas comes into contact with the test piece to start corrosion, and the test piece is discolored. Therefore, it is desirable that this discoloration be visible from the outside of the protective case.
In addition, careless contact of the test piece with a hand or adhesion of water droplets or the like to the test piece causes corrosion due to non-measurement causes. Therefore, it is desirable to protect the test piece with a cover of a protective case. Covering the test piece with a cover in this way requires an inlet / outlet port for sending the external atmosphere to the surface of the test piece. Therefore, an inlet / outlet port for the atmosphere is provided in addition to the portion covering the main surface of the test piece.

(2) A preferred protective case will be described with reference to FIGS. 3B is a base of a protective case (referred to as a set base), FIG. 3C is a cover fitted to the set base, and FIG. 3A is a state in which the cover is fitted to the set base. It represents. In addition, FIG.
FIG. 4B shows a cross section of the central portion of the protective case, and FIG.
Is a cover, and FIG. 4B is a set base.

In the figure, 11 is a side edge of the set base, and 12 is a side edge.
Is a cover, 13 is a test piece, 14 is a hole for suspending the protective case, 15 is an air inlet / outlet provided at both ends of the protective case, 16 is a convex portion for fixing the cover 12 to the set base 11, and 17 is A hole 18 for receiving the convex portion 16 of the cover 12 is a collar for promoting the inflow of air into the air inlet / outlet port 15. The entire protective case has a total length of 90 mm, a total width of 44 mm and a total height of 30 mm.

Since the surface of the test piece 13 is covered by the cover 12, it does not come into direct contact with the hands or the like, but the air inlet / outlet 15 makes contact with the environmental gas. Both ends of the test piece 13 are supported by both side edges 11 of the set base,
The test piece 13 is fixed by fitting the convex portion 16 of the cover 12 into the holes 17 of both edges 11. As shown in FIGS. 4 (A) and 4 (B), the inner width W ₁ of the set base is designed to be slightly smaller than the outer width W _{2 of} the cover 12, and the cover 12 is set by the frictional force between the side edges 11. It is preferably fixed.

The test piece 13 is fixed parallel to the bottom surface of the set base 11 so that more air can contact the surface (main surface) of the test piece 13, and the air inlets / outlets 15 are arranged on the left and right sides of the surface of the test piece 13. To do. The air inlet / outlet port 15 may be provided in either (or both) of the set base 11 and the cover 12, but in general, at least the cover 12 is made of transparent resin, and
An air inlet / outlet port 15 is provided in both the cover 12 and the cover 12.

The air inlet / outlet port 15 is preferably provided with a collar (reflecting plate: guide) 18 in order to take in as much external air as possible. In this way, since the upper part of the main surface of the test piece 13 is covered with the cover 12, water drops and the like are not covered by the test piece 13.
It can be prevented from scattering. Therefore, if this protective case is hung under the eaves, measurements can be performed outdoors. In particular, when the test piece 13 is hung by the hole 14 provided in the protective case, the main surface of the test piece 13 is oriented in a substantially vertical direction, and it is protected from rain and the like. Moreover, if this hole 14 is used, it can be easily suspended and installed indoors.

Such a protective case is preferably manufactured by injection molding of transparent AS (acrylic styrene), but it is also possible to use a polycarbonate resin or the like.

(3) The protective case shown in FIG. 3 (A) can also be used outdoors by hanging it under the eaves, but it can be used for buildings without eaves (or small buildings), riverbeds without buildings, etc. When measuring the environmental atmosphere at a place, or when the wind is strong even if it is left under an eaves, there arises a problem that rainwater splashes on the sample. Therefore,
When using it in such a place, provide an umbrella in the protective case.

Referring to FIGS. 5 and 6, FIG. 5A is a perspective view of a protective case (measurement kit) with an umbrella, FIG. 5B is a vertical cross-sectional view of the protective case with an umbrella, and FIG. 6A. And (B) is a development view of each composition part of the umbrella. This umbrella is made of a film-shaped organic material or a thin plate-shaped metal material, and covers the upper part of the environmental measurement sample 21 and a ventilation hole between the sample 22 and the umbrella part 22 of FIG. 6 (A). It is produced by assembling the sample fixing portion 23 of FIG. 6 (B) combined with the umbrella portion 22 as shown in FIG. 5 (A) so that 24 is kept above the hem of the umbrella portion 21. Here, the sample 21 may be the protective case (measurement kit) itself shown in FIG. 3A, and the sample 21 is fixed to the sample fixing portion 23 by some means. The fixing can be devised appropriately such as a string, abrasion force, and a hook.

Using this umbrella, as shown in FIGS. 5 (A) and 5 (B), the upper umbrella portion 22 of the sample 21 receives rain from above the sample, and the sample fixing portion 23 on the side surface of the sample from the lateral direction of the sample. Prevent rain. However, the air at the survey location can come in and out through the vent hole 24 provided between the sample and the umbrella portion, and therefore sufficiently contacts the sample. Since this vent is provided above the hem of the umbrella part, rain does not enter from the vent.

Since this umbrella is made of a flat material, it can be mass-produced at low cost and does not take much time to store it. Furthermore, the assembly is easy and the sample can be easily attached and detached, and the conventional sample can be used as it is. The sample and umbrella can be easily hung with a string or the like, but since the hem of the sample fixing part is horizontal, it can be placed in a place where rainwater does not collect. If at least a part of the umbrella is made transparent, discoloration of the sample can be observed at any time.

(4) The test piece is to observe and analyze the test piece after leaving it in the environment for a predetermined period for the purpose of knowing the average gas concentration for a long time, and it is desirable to shorten the leaving period. In some cases. For such a purpose, the atmosphere may be forcibly supplied to the test piece to promote the reaction between the gas in the environment and the test piece. Then, when a protective case (measurement kit) as shown in FIG. 3 (A) is attached, a device was devised to send air so that fresh air always hits the surface of the test piece. Air is sent by a blower fan,
Although there is a method of heating air to generate convection, a fan is advantageous in terms of safety and convenience.

The first mode is shown in FIGS. 7 (A) and 7 (B).
In this mode, air is taken in from one side of the device and discharged from the other side, and a test piece is arranged between them. FIG. 7A is an external view and FIG. 7B is a horizontal sectional view schematically. When a dry battery (either a solar battery or an AC power supply may be used for the purpose of eliminating battery consumption) 32 is attached to the accelerator body 31, a motor 34 connected by a conductor 33 is driven to rotate a fan 35. Therefore, when the upper cover 36 is covered, the air taken in from the air intake 37 is called an air outlet 38.
And blows out from the outlet 38 at a constant speed. The velocity of the air can be adjusted by varying the rotation of the motor 34. This is possible due to the variable resistor 39 connected in series with the conductor 33.

The protective case 10 in which the test piece 13 shown in FIG. 3 (A) is set is attached to the case attaching portion 40. Installing the test piece set in the case instead of directly mounting it on the device facilitates handling of the test piece, and at the same time causes the surface of the test piece to be inadvertently touched by hands or the like, which may cause corrosion. It has the effect of preventing this. Since the case 10 is mounted along the groove 41 provided in the case mounting portion 40, the case 10 is fixed horizontally to the accelerator 31, and the surface of the test piece is kept parallel to the air flow.

The air blown from the blow-out port 38 enters from one of the air inlet / outlet ports 15 of the case 10 to which the test piece 13 is attached.
After touching the surface of, the air comes out from the other side of the air inlet / outlet port 15. The test piece 13 reacts with the gas contained in the contacted air and exhibits a reaction result specific to the combination of the test piece and the gas. The material of the accelerator body 31, the upper cover 36, and the fan 35 is selected from organic materials that are not corroded by gas, such as acrylic resin, polycarbonate resin, and polystyrene resin. Dry battery 32, conductor 33, motor 34 and variable resistance
The accelerator 39 is protected in the accelerator body 31 from being corroded by gas.

FIGS. 8A and 8B show the second mode,
This is a device in which air is taken in from above vertically and discharged horizontally (or vice versa). 8A is an external view and FIG. 8B is a vertical cross-sectional view, and the same reference numerals are given to the same members as those in FIGS. 7A and 7B. The case 10 shown in FIG. 3 (A) is mounted vertically in the case mounting portion 40 on the top surface of the apparatus.

FIGS. 9A, 9B and 9C show FIG.
The position of the dry battery 32 is changed to the motor 3 by the deformation of (A) and (B).
4. It is placed above the fan 35 to open and close the lid 42 so that the dry battery 32 can be easily put in and out, and the device is made light and small, and the dry batteries are connected in parallel to reduce the battery consumption. . 9A is an external view, FIG. 9B is a vertical sectional view, and FIG. 9C is an electric circuit diagram.

Example 1 As shown in FIGS. 10A to 10C, silver Ag and copper C were used.
A u porous test piece was prepared. These test pieces 1 were obtained by press-molding powder having a particle shape of 50 μm into a thickness of 40 mm × 5 mm × 1 mm. The sample was then placed in a furnace with hydrogen purge at 50
Sintered at 0 ° C for 2 hours, each density 6.5 g / cm ³ ,
A porous sintered body of 6.8 g / cm ³ was obtained. Figure 10 (B),
In (C), 4 is a particle of silver or copper, 5 is a void, and 6 is adsorbed NO _x .

[0056] To examine the collecting effect of NO ₂ gas of these test pieces, and the present test piece was left for 24 hours NO ₂ gas in a desiccator introduced 10 ppm. The test piece left is NO ₂
In order to investigate whether or not the gas was captured, analysis was performed using an infrared spectrophotometer and a fluorescent X-ray analyzer. The IR spectrum of the result of the infrared spectroscopic analysis of the test piece is shown in FIG. From this figure, since the known absorption wave number for NO _x corresponds to the wave number of this analysis, it is confirmed that this test piece absorbs NO _x .

FIGS. 12 and 13 show the results of nitrogen and oxygen analysis of this test piece using a fluorescent X-ray analyzer. Figure 12
Is the X-ray intensity of O in the Cu test piece by X-ray fluorescence analysis, Fig. 11
Shows the X-ray intensity of N in the Cu test piece by fluorescent X-ray analysis. From these results, it can be seen that oxygen and nitrogen are trapped in both test pieces. As a practical application experiment for these test pieces, the test pieces were left for 1 month in a desiccator into which 10 ppb of NO ₂ gas was introduced. 5 during neglect
The test piece was taken out every day, and the X-ray intensities of nitrogen and oxygen were measured by a fluorescent X-ray analyzer. As a result, as shown in FIG. 14, the amount of trapped NO ₂ gas was small at the beginning and could not be detected, but thereafter, the amount of nitrogen and oxygen increased until 25 days, and the amount that could be analyzed was trapped. Was there.

[0058]Example 2 As in Example 1, SiO₂-XAl₂O₃(X = 0.
15) and YBa₂Cu ₃Oy Porous Ceramic Specimen
Was produced. These test pieces consist of 40 powders with a particle size of 50 μm.
It is press-formed into a thickness of 5 mm × 5 mm × 1 mm. Next
The sample was sintered at 1000 ° C for 2 hours in a furnace that was replaced with hydrogen.
Each density is 1.8 g / cm³, 2.0 g / cm³Porous ware
I got a union.

[0059] To investigate the collecting effect of NO ₂ gas of these test pieces, and the present test piece was left for 24 hours NO ₂ gas in a desiccator introduced 10 ppm. The test piece left is NO ₂
In order to investigate whether or not the gas was captured, analysis was performed using an infrared spectrophotometer and a fluorescent X-ray analyzer. The result of analyzing the test piece with the infrared spectrophotometer is the same as that in Fig. 11. Since the known absorption wave number and the wave number of this analysis correspond, it was confirmed that this test piece absorbed NO. It was In addition, the results of the analysis of oxygen and nitrogen by the fluorescent X-ray analyzer are also shown in FIG.
2. Similar to FIG. 13, it was confirmed that oxygen and nitrogen were trapped in both test pieces.

As a practical application experiment of these test pieces, NO
The test piece was left for 1 month in a desiccator into which ₂ ppb of ₂ gas had been introduced, and the X-ray intensities of nitrogen and oxygen were measured by a fluorescent X-ray analyzer in the same manner as in Example 1. The results are also similar to those in Fig. 14, which could not be detected because the amount of trapped NO ₂ gas was small at the beginning, but thereafter, the amount of nitrogen and oxygen increased until 25 days, and the amount that could be analyzed was trapped. It had been.

Example 3 First, copper powder having a particle size of 100 μm and SiO ₂ -x having a particle size of 1 μm were used.
Al ₂ O ₃ (x = 0.15) was kneaded with a ball mill to deposit fine SiO ₂ -xAl ₂ O ₃ powder on the surface of copper powder particles. This copper powder was press-formed into a thickness of 40 mm × 5 mm × 1 mm, and then sintered in a hydrogen-exchanged furnace at 500 ° C for 2 hours to obtain a test piece made of a porous sintered body having a density of 4.0 g / cm ^3. Obtained.

The internal structure of this test piece is schematically shown in FIG. Reference numeral 51 is copper particles, 52 is ceramic particles, and 53 is adsorbed nitrogen oxide. The test piece was left for 24 hours in a desiccator into which 10 ppm of NO ₂ gas was introduced, and the left test piece was analyzed using an infrared spectrophotometer and a fluorescent X-ray analyzer. The results of both the analysis of nitrogen and oxygen by the infrared spectrophotometer and the fluorescent X-ray analyzer were the same as in Example 1.

Further, as a practical application experiment of this test piece, N
Place the test piece in a desiccator containing 10 ppb of O ₂ gas.
The result of leaving for a month was also the same as in Example 1, and when the X-ray intensities of nitrogen and oxygen were measured by the fluorescent X-ray analyzer, it could not be detected because the amount of trapped NO ₂ gas was small at the beginning. After that, the amount of nitrogen and oxygen increased until 25th, and the amount that could be analyzed was trapped.

Example 4 As shown in FIG. 16, a copper piece having a large number of holes was prepared by a press molding method. Copper piece is 40mm × 5mm × 1mm thick, hole diameter is 1m
m, the formation density of holes is 25 holes / cm ² . Fine SiO ₂ -xAl ₂ O ₃ powder (particle size 10 μm) was filled in the holes. This filling is done by adding SiO ₂ · Al to a test piece with holes in advance.
₂ O ₃ powder was sprinkled into the holes to remove the excess, and then the powder was baked at 500 ° C. for 2 hours in a hydrogen atmosphere in order to fix the powder. In FIG. 16, 55 is a copper piece, and 56 is a fine ceramic particle filled in the hole of the copper piece.

This test piece was allowed to stand in a desiccator into which 10 ppm of NO ₂ gas had been introduced for 24 hours, and the left test piece was analyzed using an infrared spectrophotometer and a fluorescent X-ray analyzer. As a practical experiment, 10 pp of NO ₂ gas was used.
b Leave this test piece in the introduced desiccator for 1 month,
The X-ray intensities of nitrogen and oxygen were measured with a fluorescent X-ray analyzer.
All the results were the same as in Example 1.

Example 5 First, SiO ₂ -xAl ₂ O ₃ having a particle size of 100 μm and Cu powder having a particle size of 1 μm were kneaded in a ball mill to form SiO ₂ -xA.
Cu powder was adhered to the particle surface of l ₂ O ₃ . This ceramic powder was molded into a thickness of 40 mm x 5 mm x 1 mm, and then sintered in a furnace purged with hydrogen at 1000 ° C for 2 hours to obtain a density of 2.4 g / cm ²
A test piece composed of the sintered body of was obtained.

The test piece was allowed to stand in a desiccator into which 10 ppm of NO ₂ gas had been introduced for 24 hours, and the left test piece was analyzed using an infrared spectrophotometer and a fluorescent X-ray analyzer. As a practical experiment, 10 pp of NO ₂ gas was used.
b Leave this test piece in the introduced desiccator for 1 month,
The X-ray intensities of nitrogen and oxygen were measured with a fluorescent X-ray analyzer.
All the results were the same as in Example 1.

Example 6 A ceramic piece having a large number of holes having a shape as shown in FIG. 16 was produced by press molding. Ceramic pieces
40mm × 5mm × 1mm thickness, hole diameter is φ1mm, hole forming density is 25
The number of pieces / cm ² . Fine Cu powder was sprinkled on the ceramic pieces in the holes to remove excess powder, and then sintered in a hydrogen furnace at 500 ° C. for 2 hours to fix the powder.

In this case, in FIG. 16, 55 is a ceramic piece and 56
Is Cu powder filled in the holes of the ceramic pieces. This test piece was allowed to stand in a desiccator containing 10 ppm of NO ₂ gas for 24 hours, and the test piece that had been left standing was analyzed using an infrared spectrophotometer and a fluorescent X-ray analyzer, and a practical application experiment was conducted. As the test piece, the test piece was left for 1 month in a desiccator containing 10 ppb of NO ₂ gas, and the X-ray intensities of nitrogen and oxygen were measured by a fluorescent X-ray analyzer.

All the results were the same as in Example 1.

Example 7 As in Example 1, a copper Cu porous test piece was prepared.
This test piece is made of Cu powder with a particle size of 50 μm, 40 mm × 5 mm × 1
It is press-formed to a thickness of mm. Next, this sample was sintered at 500 ° C. for 2 hours in a furnace with hydrogen substitution, and the density was 6.8.
A porous sintered body of g / cm ³ was obtained. Next, this copper piece was immersed in triethanolamine for 24 hours to sufficiently permeate the inside of the sintered body.

This test piece was allowed to stand in a desiccator into which 10 ppm of NO ₂ gas had been introduced for 24 hours, and the left test piece was analyzed using an infrared spectrophotometer and a fluorescent X-ray analyzer. As a practical experiment, 10 pp of NO ₂ gas was used.
b Leave this test piece in the introduced desiccator for 1 month,
The X-ray intensities of nitrogen and oxygen were measured with a fluorescent X-ray analyzer.
All the results were almost the same as in Example 1.

Example 8 As shown in FIGS. 10 (A) to 10 (C), a Tb ₂ O ₃ porous test piece was prepared. This test piece is made of powder with a particle size of 50 μm.
It is press-formed into a thickness of 40 × 5 × 1 mm. Next, this test piece was sintered in a furnace replaced with hydrogen at 500 ° C. for 2 hours,
A porous body having a density of about 2.7 g / cm ³ was obtained.

[0074] To investigate the collecting effect of the CO ₂ gas in the test piece, and the present test piece was left for 100 hours the CO ₂ gas in a desiccator introduced 10 ppm. An analysis using XPS was performed to examine whether or not the test piece left to stand adsorbed CO ₂ gas. As a result, the C ls spectrum shown in FIG. 17 has four states [CO ₃ , CO ₂ , CO, (C-C, C-
H)] was present, and it was confirmed that CO ₂ gas was present.

As a practical application test of this test piece, the test piece was left for 1 month in a desiccator containing 10 ppm of CO ₂ gas. Remove the test piece every 10 days during
Quantitative analysis was performed on S. As a result of continuing the experiment,
As in 18, the amount of CO ₂ increased with time, and the amount that could be analyzed was trapped.

Others such as Eu ₂ O ₃ , Gd ₂ O ₃ and Tb
As a result of the same investigation using ₂ O ₃ , Tb ₄ O ₇ , Dy ₂ O ₃ and Ho ₂ O ₃ , the same adsorption effect as in the case of using Tb ₂ O ₃ was confirmed as shown in FIG. .

Example 9 As described above, it was found that a specific chloride, such as CuCl or AgCl, is effective as an SO ₂ selective scavenger (test piece). Since it is intended to be handled at a place, it must have good durability and good adhesion between the compound and the base material. for that reason,
We chose metal as the base material. Next, a method for producing a test piece that improves the adhesion between the compound and the metal was examined. The various methods examined are shown below.

The powdery compound is solidified and attached to the metal surface with an adhesive or the like. The powdery compound and the powdery metal are mixed and solidified. A compound is formed as a corrosive substance on the metal surface.

As a result, the test piece prepared in (1) is liable to return to the powder state when the compound is broken during handling. In the next test piece, depending on the method of hardening, the compound is embedded in the metal, or the surface of the metal oxide is covered with the metal oxide to prevent the compound from forming a sulfate. It turns out that this is not an effective method. On the other hand, the following method was found to be effective.

It has been found that metals corrode in a single chlorine gas atmosphere. Especially in the dry state (humidity 10% RH or less), only CuCl is used for copper and Ag is used for silver.
The inventor has found that only Cl is produced. Therefore, a test piece was produced in the following process by utilizing this corrosion reaction. (1) Prepare a device that can dilute the gas stably and a container to make the diluted gas atmosphere uniform, and create an atmosphere with a dry chlorine gas concentration of 10 ppm.

(2) Copper and silver plate (40 × 5 × 0.3 mm)
The surface oxides and rust preventives are removed by polishing with a grindstone, and ultrasonic cleaning is performed with alcohol or acetone to remove the polishing powder. (3) The copper or silver plate is left in the atmosphere prepared in (1). (4) After being left for 40 hours, the silver and copper plate on the surface of which AgCl or CuCl was formed is taken out.

(5) The removed silver and copper plates are shown in FIG.
It is stored in a case as shown in FIG. Then, in order to prevent alteration of AgCl or CuCl on the surface, it is stored in a dry nitrogen atmosphere until it is left in an actual environment. It was confirmed whether the SO ₂ gas was actually collected by the manufactured test piece (measurement kit). Therefore, the humidity is 10, 30, 50,
Atmospheres of 70, 90% RH, SO ₂ gas concentrations of 1 ppm, 100 ppb, and 10 ppb were created under a total of 15 conditions, and the test pieces were left in the atmosphere for 1 month. After leaving, it was confirmed by the following method.

(1) Confirmation by X-ray microanalyzer (XMA). XMA enables qualitative and quantitative analysis of various elements. Therefore, oxygen (O) and sulfur (S) should be confirmed when the metal surface of the collection kit left in the SO ₂ gas environment is changed to Ag ₂ SO ₃ , Ag ₂ SO ₄ , and CuSO _4. Therefore, a qualitative analysis was performed. As a result, the following results were obtained under all humidity conditions.

[0084] In addition, H ₂ S or NO ₂ was used to create the same atmosphere as SO _{2 in} both concentration and humidity, and the same confirmation was performed, and the humidity was 70%.
O was only confirmed in the test piece in which the compound was CuCl at RH and 90% RH. It is a result of standard oxidation energies of CuCl and CuO being almost the same value and being oxidized by the influence of moisture in humidity. Therefore, the principle of collection and the actual experimental results are in good agreement, demonstrating the validity of the present invention.

(2) Confirmation by X-ray diffraction (XD) By X-ray diffraction, it is possible to identify what is the product on the metal surface.
It So SO₂Of the metal of the test piece left in the gas environment
Ag on the surface₂SO₃, Ag₂SO_Four, CuSO _FourIs actually
I confirmed that it was made. As a result, in which environment
Both of the two types of test pieces left unattended have a shape similar to the sulfate shown here.
The product of was confirmed.

(3) Preparation of calibration curve In quantitative analysis of XMA, S of test pieces left under these 15 conditions was analyzed.
I investigated the amount of atoms. As a result, C
Since it was found that the amount of S atoms in both uCl and AgCl was constant, the relationship between the SO ₂ concentration and the amount of S atoms was clarified, and a calibration curve could be created.

A calibration curve of a test piece using AgCl is shown in FIG.
Shown in 20. For comparison, the conventional method (JIS K-0103) and this test piece were allowed to stand, the SO ₂ gas concentration (ppb) was measured, and both were compared. The results are shown below. Measurement area A (factory area) B (residential area) C (overseas) Conventional method 83 26 46 Invention 80 30 50 In addition, the same results could be obtained by using CuCl as a test piece.

From these results, it was confirmed that the same value as the conventional value was obtained with this test piece. As described above, as can be seen from these examples, SO ₂ could be collected by this test piece. Also, leave it in an environment where the gas concentration is changed
Since a calibration curve was created by XMA quantitative analysis, it can be used for actual measurement.

Example 10 A test piece 13 for environmental gas measurement set in a protective case 10 for environmental investigation shown in FIG. 3A (the one set in the case is called a test piece kit) is simplified. In order to investigate the effect of the umbrella used as a type environmental measurement sample, an environmental survey was conducted outdoors in a typical ordinary house in an urban area. Cu, Ag,
Al, Fe, and Fe-Ni were used as test pieces. Three sets of test piece kits were prepared, and one set was hung by passing a string through a hole 14 provided in the case on the back side of a large area under the eaves where rain does not enter. Another set was equipped with the umbrella of the present invention and hung on a clothesline in the garden facing the eaves. The rest of the set was hung as it was on a clothesline. There was no roof on the clothesline to avoid rain, so it was exposed to the rain. It should be noted that the portion of the hole 14 of the umbrella can be made liquid-tight by viscosity or the like, if necessary.

These test strip kits were left for one month. It rained several times during the neglected period. Fluorescent X after leaving
The X-ray intensity of oxygen O, sulfur S, and chlorine Cl in the corrosion product on each test piece was measured using a line analyzer. The results are shown in FIGS. 21 (A), (B) and (C). Since the air inlet / outlet 15 of the case was vertically upward, the rain entered the sample exposed to the rain without the roof and the umbrella, and the rain came into contact with the sample. Therefore, as shown in FIGS. 21 (A) to 21 (C), it was significantly corroded as compared with the sample under the eaves due to contact with rain, which is a corrosive factor other than gas. In addition, Cl was washed away by rain, and accurate measurements could not be obtained. But,
The amount of corrosion of the sample under the eaves and the sample with the umbrella attached were almost the same. That is, it was confirmed that the umbrella completely avoided rain, and sufficient air was supplied to the sample to perform accurate gas measurement.

Example 11 To confirm the effect of the apparatus shown in FIGS. 7 (A) and 7 (B), a dry battery was attached in order to investigate the relationship between the wind speed at the upper part of the test piece and the reactivity between the gas and the test piece. The wind speeds above the test piece were 0.1 m / s, 0.2 m / s, 0.3 m / s, 0.4 m / s, and 0.
5 m / s, 0.6 m / s, 0.7 m / s, 0.8 m / s, 0.9 m / s, 1.0 m / s
A device adjusted so that and a device without a dry battery were prepared. Eleven sets of silver Ag, which reacts remarkably with hydrogen sulfide H ₂ S gas and forms a compound with sulfur S on the surface thereof, as test pieces, were set in a case, and mounted on the apparatus. These were introduced with H ₂ S gas at 10 ppm. After being left for 2 weeks in a desiccator at a temperature of 20 ° C. and a humidity of 80%, each test piece was analyzed. In the analysis, the fluorescent X-ray analyzer was used to measure the X-ray intensity of S in the compound formed on the Ag surface.

FIG. 22 shows the result. Since the X-ray intensity represents the amount of S present, it can be seen from FIG. 22 that the reaction between the gas and the test piece is better when the gas is supplied to the test piece at a certain speed and brought into contact with the test piece than when it is left as it is. It was proved that the quantity would be large. It was also found that there is a wind speed at which the reaction between Ag and H ₂ S gas is most promoted, and the value is 0.8 m / s.

Next, those set in the case of Ag as a test piece 2 set prepared, one intact and the other was attached to the apparatus in which the wind speed of the test piece top is 0.8 m / s, H ₂
The sample was allowed to stand for 1 month in a desiccator containing 10 ppm of S gas at a temperature of 20 ° C. and a humidity of 80%, taken out at appropriate times, and the X-ray intensity of S was measured. The result is shown in FIG. From this figure, it can be seen that the reaction amount of Ag and S in the case attached to the device reaches the reaction amount of Ag and S in the case not attached to the device for one month in 3 weeks. , By this device,
The effect of promoting the reaction between the gas and the test piece was confirmed.

Example 12 In order to confirm the effect of the apparatus shown in FIGS. 8A and 8B, two sets of Ag as test pieces set in a case were prepared in the same manner as in Example 12, and one of them was prepared. As it is, the other is attached to the device adjusted using the variable resistor 39 so that the wind speed above the test piece becomes 0.8 m / s from the result of FIG. 22,
10 ppm of H ₂ S gas was introduced. Leave it in a desiccator with a temperature of 20 ° C and a humidity of 80% for 1 month, and take it out as appropriate.
The line strength was measured.

The results are shown in FIG. From this figure, it can be seen that the reaction amount between Ag and S in the case attached to the device reaches the reaction amount between Ag and S in the case not attached to the device for one month in two weeks. , By this device,
The effect of promoting the reaction between the gas and the test piece was confirmed. Example
In Example 13, as a result of improving the structure of Example 12 in which the case and the air intake were separated and the gas was trapped in the inner wall of the apparatus and the fan, the effect of promoting the reaction became large.

Example 13 The effect of the apparatus shown in FIGS. 9A, 9B and 9C was confirmed as follows. With the dry cell 32 attached, the wind speeds above the test piece were 0.15 m / s, 0.25 m / s, 0.45 m / s, and 0.65 m / s, respectively.
s, 1.00 m / s, 1.30 m / s each adjusted device
A stand and two devices (referred to as,) to which the dry battery 32 is not attached were prepared. Eight sets of copper Cu and silver Ag, which are reacted with hydrogen sulfide H ₂ S gas remarkably to form a compound with sulfur S on the surface thereof, were set in the case as test pieces,
Each was attached to the device. These are mixed with H ₂ S gas at 100
Introduced ppb. Each test piece was analyzed after being left for 2 weeks or 1 month except in a desiccator having a temperature of 25 ° C. and a humidity of 60%. In the analysis, the fluorescent X-ray analyzer was used to measure the X-ray intensity of S in the compound formed on the Cu and Ag surfaces.

The results are shown in FIGS. 25 and 26. The X-ray intensity represents the abundance of S. From Fig. 25 and Fig. 26, 0.15 m
It was found that if a test piece was exposed to a wind speed of / s for 2 weeks, the same amount of corrosion as that left for a month as in the past can be obtained. Example 14 is characterized in that dry batteries are connected in parallel to reduce the consumption of dry batteries, and in consideration of the arrangement of each part inside the device, the dry batteries can be easily attached / detached and the device main body is made small and lightweight. is there. Also, if the shortened exposure period is set to 2 weeks and the wind speed is set to 0.15 m / s, the same amount of corrosion as when left for 1 month can be obtained, and it is possible to correspond to the data accumulated in the past. It can be used effectively.

[0098]

[Effects of the Invention] It is inexpensive, small, and can be used in any environment where the environment
Constant gas (especially NO_X, CO₂Or SO ₂ Etc.) average concentration
It's been a problem recently because you can easily monitor the degree
Not only for the purpose of measuring environmental pollution, but also for various precision equipment.
It can be used to evaluate the installation environment of electronic equipment.

[Brief description of drawings]

1 is a principle diagram illustrating the method of the present invention in relation to NO _x .

FIG. 2 is a schematic view showing a state (measurement kit) in which a test piece according to the present invention is housed in a case.

FIG. 3 is a detailed view of a measurement kit similar to that of FIG.

FIG. 4 is a sectional view of a measurement kit similar to that in FIG.

FIG. 5 is a detailed view showing an umbrella for a measurement kit.

FIG. 6 is a development view of a portion of an umbrella for a measurement kit.

FIG. 7 is a schematic diagram showing an embodiment of an acceleration test device combined with a measurement kit.

FIG. 8 is a schematic diagram showing an embodiment of an acceleration test device combined with a measurement kit.

FIG. 9 is a schematic diagram showing an embodiment of an acceleration test device combined with a measurement kit.

FIG. 10 is a schematic diagram of a test piece for NO _X measurement and its inside.

FIG. 11 is an infrared spectrum diagram for analyzing NO _X adsorbed on a porous copper test piece.

FIG. 12: Oxygen (O) in a copper test piece by X-ray fluorescence analysis
It is a figure which shows the X-ray intensity of.

FIG. 13: Nitrogen (N) in a copper test piece by X-ray fluorescence analysis
It is a figure which shows the X-ray intensity of.

FIG. 14 is a diagram showing the relationship between the time period during which a copper test piece was left in NO _x gas and the fluorescent X-ray intensities of adsorbed oxygen (O) and nitrogen (N).

FIG. 15 is a schematic diagram showing an internal structure of a test piece obtained by kneading copper powder and fine ceramics powder and firing the mixture.

FIG. 16 is a schematic view of a test piece formed by forming a large number of holes in a copper piece.

FIG. 17 is an XPS analysis spectrum diagram after CO ₂ is adsorbed on a porous Tb ₂ O ₃ test piece.

FIG. 18 is a diagram showing the relationship between the CO ₂ strength and the period during which a porous Tb ₂ O ₃ test piece was left in a CO ₂ atmosphere.

FIG. 19 is a diagram showing a relationship between a CO ₂ adsorption amount and a standing period when various rare earth oxides are used.

FIG. 20 shows a calibration curve for SO ₂ measurement using silver chloride.

FIG. 21 shows the results of analysis of corrosion products on test pieces when the measurement kit is placed under the eaves, in the garden (with an umbrella), and in the garden (without an umbrella).

FIG. 22 is a diagram showing the amount of sulfur (S) reacted with a test piece when air was sent to the silver test piece at a predetermined speed.

23 shows the amount of sulfur reacted with a test piece using the accelerator shown in FIG.

24 shows the amount of sulfur reacted with a test piece using the accelerator shown in FIG.

FIG. 25 is a period of time during which the copper test piece was left alone and sulfur (S) reacted with the test piece when the wind speed was changed in the accelerator shown in FIG.
It is a figure which shows the relationship of the amount of.

FIG. 26 is a standing period of a silver test piece and a sulfur (S) reacted with the test piece when the wind speed is changed in the accelerator shown in FIG.
It is a figure which shows the relationship of the amount of.

[Explanation of symbols]

 1 ... Test piece 2 ... Ceramic particle 3 ... Nitrogen oxide 4 ... Ceramic particle 5 ... Gap 6 ... Adsorption gas 10 ... Protective case (measurement kit) 11 ... Set base 12 ... Cover 13 ... Test piece 15 ... Air inlet / outlet 21 ... Sample (Protective case) 22 ... Umbrella part 23 ... Sample fixing part 31 ... Accelerator body 32 ... Dry battery 34 ... Motor 35 ... Fan 40 ... Case mounting part 41 ... Case mounting groove 42 ... Lid

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Michiko Sato 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited (72) Inventor Shigeru Fukushima 1015, Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited ( 72) Inventor Yasuo Ueda, 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa, Fujitsu Limited (72) Inventor Takashi Furusawa, 1015, Kamikotanaka, Nakahara-ku, Kawasaki, Kanagawa Fujitsu Sinter Limited (72) Inventor, Tsutomu Iikawa Kanagawa 1015 Kamiodanaka, Nakahara-ku, Kawasaki-shi, Japan Within Fujitsu Limited (72) Inventor Shunsuke Kitakoji 1015 Kamikodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Within Fujitsu Limited (72) Inventor Teruo Motoyoshi Nakahara-ku, Kawasaki-shi, Kanagawa 1015 Kamiodanaka, Fujitsu Limited

Claims (30)

[Claims] 1. A metal or ceramics or metal salt test piece
Is placed in an ambient atmosphere to be measured, and after a predetermined time has passed, the
NO adsorbed on the test piece_X, CO₂ Or SO ₂A fixed amount
NO in the ambient atmosphere_X, CO₂Or SO₂ Inspect
A method for measuring an environment characterized by determining. 2. The method according to claim 1, wherein the test piece is a porous metal or ceramic test piece, or a test piece in which fine metal or ceramic powder is carried on an integral metal or ceramic piece. 3. The porous or finely divided metal is copper, silver,
It is one of platinum, rhodium, ruthenium, palladium, iridium, and nickel, and NO _x in an environmental atmosphere.
The method according to claim 2, wherein 4. The porous or fine granular ceramics
SiO₂-Al₂O ₃, YBa₂Cu₃O_x, Cr
O₂, Cr₂O₃, Fe₂O₃, Co₂O₃, Sn
O₂, CoAl₂O_Four, CuO, Al₂O₃, Of MgO
It is either NO in the environmental atmosphere_xClaim to test
The method according to item 2. 5. a specimen filled with triethanolamine in the air gap of the test piece porous metal or ceramic pieces, The method as in claim 2 wherein wherein assaying the NO _x in the ambient atmosphere. 6. The test piece is porous La ₂ O ₃ , Ce.
₂ O ₃ , Pr ₂ O ₃ , Nd ₂ O ₃ , Pm ₂ O ₃ , Sm _{2
O 3, Eu 2 O 3,} Gd 2 O 3, Tb 2 O 3, Tb 4 O
₇ , Dy ₂ O ₃ , Ho ₂ O ₃ , Er ₂ O ₃ , Tm
The method according to claim 1, which is a test piece of a metal oxide selected from ₂ O ₃ , Yb ₂ O ₃ and Lu ₂ O ₃ , and which tests CO ₂ in an ambient atmosphere. 7. The method according to claim 1, wherein the test piece is made of a metal chloride having a free-form energy of chloride> sulfate, and is assayed for SO ₂ in an ambient atmosphere. 8. The method of claim 7, wherein the metal chloride is copper chloride or silver chloride. 9. Placing two or more test pieces in an environment,
O _x, CO _2, The method as in claim 1 wherein assaying two or more of SO _2. 10. NO _x , CO ₂ or S in an ambient atmosphere
NO _x in an environmental atmosphere, comprising a metal or ceramics or metal salt test piece for selectively adsorbing O ₂ , and a case for leaving the test piece in an environment atmosphere to be measured, A measurement kit for assaying CO ₂ or SO ₂ . 11. The measurement kit according to claim 10, wherein the test piece is a porous metal or ceramic test piece, or a test piece in which fine metal or ceramic powder is carried on an integral metal or ceramic piece. . 12. The porous or fine-grained metal is copper,
One of silver, platinum, rhodium, ruthenium, palladium, iridium, nickel, NO in the environmental atmosphere
The measurement kit according to claim 11, which tests _x . 13. The porous or fine-grained ceramic is SiO ₂ —Al ₂ O ₃ , YBa ₂ Cu ₃ O _x , CrO.
₂ , Cr ₂ O ₃ , Fe ₂ O ₃ , Co ₂ O ₃ , SnO ₂ ,
It is any one of CoAl ₂ O ₄ , CuO, Al ₂ O ₃ and MgO, and tests NO _x in an ambient atmosphere.
The measurement kit according to item 1. 14. The measurement kit according to claim 9, wherein the test piece is a test piece in which voids of a porous metal or ceramic piece are filled with triethanolamine, and NO _x in an environmental atmosphere is assayed. 15. The test piece is porous La.₂O₃, C
e₂O₃, Pr₂O ₃, Nd₂O₃, Pm₂O₃, Sm
₂O₃, Eu₂O₃, Gd₂O₃, Tb₂O ₃, Tb₃
O₇, Dy₂O₃, Ho₂O₃, Er₂O₃, Tm₂O
₃, Yb₂O ₃, Lu₂O₃Of metal oxides selected from
It is a test piece and CO in an environmental atmosphere₂Claim to test
The measurement kit according to item 10. 16. The measurement kit according to claim 10, wherein the test piece is made of a metal chloride having a free-form energy of chloride> sulfate, and is used for assaying SO ₂ in an ambient atmosphere. 17. The measurement kit according to claim 16, wherein the metal chloride is copper chloride or silver chloride. 18. NO _x , comprising two or more of the test strips,
A claim for testing two or more of CO ₂ and SO ₂ .
The measurement kit according to item 10. 19. Further, copper, silver, aluminum, iron and
The measurement kit according to claim 10, comprising a test piece of at least one metal of 52 alloys. 20. A test piece comprising a base carrying a test piece made of a metal, a ceramic or a metal salt for calibrating an environmental atmosphere, and a cover attached to the base so as to cover the test piece. The cover or base portion covering the main surface is transparent, the main surface of the test piece can be seen from the outside, and the atmosphere gas inlet / outlet port is provided at a position other than the portion covering the main surface of the test piece. Environmental protection test piece protection case. 21. The test piece is placed on the base so that the main surface of the test piece is parallel to the bottom surface of the base, and a transparent resin cover is attached to the base so as to cover the main surface of the test piece. However, the atmosphere gas inlet / outlet is provided on both sides of the main surface of the test piece so that the atmosphere flows in parallel to the main surface of the test piece, and a collar for promoting the inflow of the atmosphere into the atmosphere gas inlet / outlet is provided. The test piece protection case according to claim 20. 22. The test piece protection case according to claim 20, further comprising a rain and snow protection umbrella. 23. The test piece protection case according to claim 20, further comprising means for forcibly feeding atmospheric gas from the environmental atmosphere to the main surface of the test piece. 24. The test piece protection case according to claim 23, wherein the atmospheric gas supply means is a fan driven by a power source. 25. The test piece protection case according to claim 20, wherein a test piece is mounted. 26. A sample fixing portion for accommodating a protective case of a test piece for measuring ambient gas, and an umbrella portion for covering the sample fixing portion to protect the test piece from rain, snow, etc., and the sample. An umbrella for a test piece protection case, comprising an air inlet / outlet port for the test piece of the test piece protection case housed in a fixed portion. 27. The umbrella portion is formed of a conical plate-shaped member, and the sample fixing portion is formed of a plate-shaped member to accommodate a sample and a plurality of arm portions extending from the top of the conical portion. 27. The umbrella for a test piece protective case according to claim 26, wherein the sample fixing portion has a structure attached to the umbrella portion by the arm portion. 28. An air inlet and an air outlet are provided, and a sample housing portion and a fan for housing a protective case of a test piece for measuring ambient atmosphere gas are provided in a communication space extending from the air inlet to the air outlet. A forced air blower for a test piece protective case, wherein the fan can form an air flow from an air inlet to an air outlet. 29. The battery is driven by the fan.
A forced air blower for the test piece protection case described in 28. 30. The forced air blower for a test piece protective case according to claim 28, wherein the fan is driven by a solar cell.