JPS604201A - Moisture sensitive element - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a humidity sensing element useful for determining humidity by detecting changes in humidity as changes in the humidity. More specifically, the present invention has excellent characteristics in that the electric torsion changes quickly in response to changes in temperature and humidity, and the electric resistance changes within a practical setting and static range in accordance with changes in humidity.
For example, when the relative humidity changes in the range of about 80 to about 30%, the electrical resistance changes in the appropriate order of about to' to 105 Ω, and it is inexpensive and easy to manufacture. The present invention relates to a moisture sensitive element based on iron oxide.

Conventionally, many moisture-sensitive elements have been proposed, such as those in which a porous matrix is infiltrated with an aqueous solution of lysate, and those in which metal oxides are used.

An example of a moisture-sensitive element in which a porous matrix is infiltrated with an electrolyte water bath solution;
Impregnated porous matrices such as resin foam are listed as >a+. For example, see Kiyoshi Takahashi, "Introduction to Senza Technology," Kogyo Kenkyukai, first edition, pp. 132-134 (1978). Moisture-sensing elements using an electrolyte of ζ are sensitive to temperature; for example, if left unused for 6 months at a temperature of 35°C or higher, the characteristics will change significantly and become unusable; , there are drawbacks such as ``Kika'' being washed away.

Moisture sensing elements using gold oxides include, for example, (α) those using ferroelectric LiNbU crystals (Patent Publication No. 55-22122), (b) lithium niobium or tantalum. Glass of brewed lithium powder 4
Sintered material with finished material (Shikai 57-8070)
(C) Lithium Naromiya metal oxide yarn component first wood, such as LiNbU, glass powder and Fg,
(3111 such as /, , C'r, 0., Ga, 03
A product obtained by sintering the #1 product containing metal oxide C + powder of η (%Kaikai Publication No. 57-207301, %opening 5).
7-210604 Publication), (')” rt OB
,” than metal oxide porcelain such as 02 and MQO.
A large number of products are known such as J:, wet resistor elements, etc., but these conventional gold oxide materials have not been fully developed.
, Mizotsuko is physically, chemically, and thermally cheap, but in general, it has a high mukaiichi wa It is the inner tightening to make it Akita at the same time.

Therefore, the present inventors conducted intensive research to find a moisture-sensitive element that does not have any drawbacks, and as a result, Kinjo oxidized starch, which has iron, niobium, and lithium as metal components, is subjected to μL condensation under specific conditions. The sintered body that exhibits t) MoriM-like X-ray diffraction and lean obtained by this process is i+Ji! Due to the responsiveness of electrical resistance to changes in U), the air resistance changes in a practical range following changes in humidity, and the humidity can be extracted using a h-sensing circle. He submitted a wet moisture-sensitive element, discovered scales, and completed the book.

Therefore, according to the present invention, the material is made of a sintered body of gold-tin panodide 1 containing iron, niobium and lithium as gold i1 components, and the diffraction angle 2θ- of the X-ray diffraction pattern by α rays is Jj+- is provided with a Q+ characteristic having a characteristic peak at 29.5°±0.2°.

The sintered body according to the invention can be prepared from niobium oxide (I2) and lithium oxide (601) by firing in a manner known per se.

~, 1-total, 1-harvest tdl'eO, fi''
e203, P' g.

In addition to 04, iron-containing Htel, which can be converted to iron oxide under an atmosphere of 6 meters of oxygen-rich gas, 91 Eli/
'e ((,'0.n2FeS, etc.), each of which can be used alone, or two or more types may be used in combination.

As a source of niobium oxide, for example!・,j:,NbUSIV
In addition to bO,, Nb, and OLl, there are also niobium-containing compounds that can be converted to niobium oxide by firing in an atmosphere of 1 J of oxygen-containing gas, such as IVb ((,l#), , IVbBr, ,
Examples include JVbF, , Nb1lSNbc, and NbN, and each of these can be used alone or in combination of 2 ai or more.

In addition, as 1′γ lithium W, 6・1j(dS
In addition to Li02, there are other lithium compounds, such as Vi/z2G', which can be sintered into lithium oxide when exposed to alcoholic gas.
0. ,LiOH,LiBC'U, ,LiclSLi
clO,, LiBr, Li1%LiF%Li, SO,
, LiJiSO, , LiN0. , LiN11. , Li
BB, , Li, S, %LiE, Li5N, Li
.

Examples include C, , C, 04Li2, etc., and each of these can be used alone, or two or more yuzu or more can be used in combination.

Furthermore, as a common source of niobium oxide and lithium oxide, for example, LiNb0. , Li1Nb□O? I, Li
For IVb308, Li, IVbU4ti&fiu-
I can also do it.

L￥L; side + A oxide 5I・>(#M, li)
The production of a sintered body from a sintered body can be affected by forces Z- and L of 1.r. With one sword, one power, one person, V, the three divine metals of iron, niobium, and lithium.
By mixing the chemical source in powder or granular form at the same time and pulverizing it thoroughly as necessary, after preparing a rice hydrate with a grain size of P)+'N, it is mixed with 1 Niwanoki. mold things,
) can be fused. It's a reed, there's another way.
The oxidation qxt+% of the three gods IJ4, iron, niobium and lithium, is 1:) of any two ears of gold cake, such as a niobium oxide source and a lithium oxide source or an iron oxide source. A niobium oxide source is mixed with the niobium oxide source, thoroughly pulverized with 8 hard, then molded, and once fired at a temperature of about 600 to about 1,500°C, preferably about 600 to about 1,300°C, and the resulting sintered body is The resulting powder mixture is re-molded and sintered. You may also do so.

In these methods, the raw material mixture is pulverized using an 8-hand pulverizer such as an Eva-ball mill or a vibration mill.
The particle size of the powder mixture during molding is generally about 0.05 to about 200 microns. L < +-IJI 0.1-i+ 60
It can be made with a grain having an average particle size of microns.

The netsuke allocation of each /1i)t@tinoxide or two will increase depending on the amount of tl to be added to the final product, but in general, the atomic ratio of each of the metals 1 (dt rH,
j, te, (ct) iron 40~! + 8.9 atom %, preferably Ita 6 (1 to 989 atoms, (b) niobium 1 to 30 atoms, preferably 1 to 20 atoms, (C) lithium 0.1 to 30 atoms, preferably 1 Or 0.1
~201IJt child b However, (α) + (b) + (C) single needle is 10
Assuming that there are 0 atoms, it is appropriate to mix in the following ratio.

(l) The lip made of silk in this way) rounding the end 9 Of course, it is also possible to use a press molding tool to cut and remove the lip, and the lip) may be formed without pressure depending on the case. can. When press forming, the pressure fitting is generally 50 to 2000 to 9/
d, the range of phantom 1 or 500 to i 5 U Oh/Ca is common.

In addition, when it comes to molding, a binder can be added to the rice water droplet. As the caking agent 11 that can be used, it is suitable to use a material that burns under the sintering conditions described above and does not leave any residue (f%). Methacrylate yarn co-coherent, polyethyl acrylate, ethyl acrylate-based 1'11' H form, 7j! Cellulose, gelatin, methyl cellulose, methyl ether cellulose The amount of these binders is not strictly limited and can vary widely depending on the type of binder, but in general 100 pieces of powdered water *0 per igli.

5-40, -@j part, preferably 0.5-2O
It can be used in Jlt area allocation.

The molded mixture is then fired. During the firing, approximately 60
Preliminary firing is performed at a temperature of 0 to approximately 1,500°C for a period of time, e.g., 5 minutes to 5 hours, and the preliminarily fired product is crushed, and then heated.
Finally, it can be baked. This pre-firing → crushing → molding process may be repeated two or more times as desired, thereby making it possible to burn one piece of baked 11' in one piece.

The machete to obtain the final sintered body:
Generally, a temperature range of about 1100°C to about 1500°C, from about 1150°C to about 1350°C, is used. The time at that temperature is approximately 1,000 degrees.For example, at 1200"G, it is approximately 10 minutes at K in degrees.
Approximately 2 inches, at a temperature of 1270°C it will take approximately 3 minutes to approximately 11!
i interval is appropriate.

Calcination can generally be carried out in air, but if necessary, it can also be carried out in an I-silicon-containing gas atmosphere enriched with I-silicon.

By another method, 11- is applied as described in iiJ) by adding the above-mentioned binder and a suitable solvent to the raw material with water, which has been removed, for coating. A slurry or paste of a sopping viscosity is prepared, and this is mixed with, for example, alumina,
beryllia, silica, forsterite, steatite,
After applying it to a desired refractory substrate such as mullite, magnesia, sorconia, cordierite, purple silicon, boron nitride, etc. to form a film of about 0001 to about 1P (dry state), This may be fired under the temperature and time conditions f'4- as exemplified above to produce a fired body on the substrate.

The sintered body generally produced as described above is substantially composed of iron, niobium, lithium, Q & A J components (7), and gold and @ oxides, and the composition of the metal oxides is Corresponding to the charged raw materials, the following ratio is converted to the gold stripe atomic ratio of iron, niobium and lithium: (α) Iron 40 to 9 atomic parts, preferably 60 to 98.9 atomic parts (6) Niobium 1 to 30 atoms, preferably 1 to 20 atoms (6) Lithium 0.1 to 30 atoms, preferably 0.
1 to 20 atoms H1 in (α) + (b) + (c) is l
001J:,', Assume that it is a child.

Also, this book C5su J's firing i)
;,,(゛times 1 nodogu turnre (therefore, Q: I&χtsur
frarLru. That is, in the X-attached diffraction pattern of the sintered body of the present invention due to C'u-human alpha rays, Fe, 03, and Linb, which can be omitted as the main body of the body, are
Adding the force 11 to the peak due to r and S, the diffraction angle 2θ=
29.5° ±0.2° q eyebrow 1 beak all south -. This turning angle 2θ = 29.5° ± 0.2° Beekts rotation u
l'3J+j and (summer) is kre+JA51〈preferably, /' e, 0. 2θ-24,2
Intensity ratio of diffraction 'jiiiU(+2)'+/
It is generally Q, 05 to 0.7, preferably 0.1 to
It is appropriate that it be within the range of 0.6. Intensity ratio 'I/+
2 exceeds 0.7 f: The rate of change in the electrical resistance of the sintered body with respect to changes in humidity is relatively small, and the humidity sensitivity tends to deteriorate, so it is not preferable to shake it. .

However, according to this Sanmei, 4j → provided pyoumi;
C-, 11i" ′φ electrical resistance changes rapidly in response to the change in degree D'J'L6 Answer 1'J-, so that O・9,■ta,lH1Exhibition V Follow Electrical resistance is put into practical use (''・
It has excellent characteristics as a moisture sensing element, such as changing in a positive range, such as room no-fu for Junkai, mochi conditioner for deer, car air conditioner, etc. Dryer,
Widely used in humidifier bamboo applications.

The humidity sensing element of the present invention is used in these applications, and the sigma element is used by being modified by means known per se. As a means of forming electrodes,
For example, a method such as a screen printing method, a coating method, a dipping method, a #deposition method, or a sputtering method can be used. In addition, the shape of the electrode can be selected as appropriate, such as a comb-shaped electrode,
It can be provided in the shape of a spiral box, object, or parallel electrodes.

Examples of electrode forming materials include Au, At, Pd, and A.
g, Jg-pu, all poles of + to C'uS8i- and Rqt
02, LaC'rO.

It is possible to use chemical resistant materials such as

Hereinafter, 釆／11・Iし１】 +: Makes 1 wisdom even more important.

Implementation Reli l~4 and Comparative Example 1 f&t1Ma (p'e2g shown in 41'fi, and Li
'I'
) J 4'7・(Niji' marked. C powder mixture (C caking i11 as powder bed mixed '1' 1007i + 5 per part)
11': Dopa l;'s] Lanoin Kyuriki ■ Etenkon 1 o, about 1 ton/crd j toka ('iE 20 #
1IIi% JIJ' It was pressed into a disc shape with a diameter of about 1 mm. The obtained disk-shaped NE・F was heated to 1150℃~12
Heat treatment was carried out at a temperature of 50° C. for about 20 minutes to about 31 minutes, and the firewood was packed. Screen E' is integrated into the grilled chicken.
4. Print a (16-type 'Kameyu') using gold paste using the paulownia method, and bake it at about 850℃ for about 45 minutes to create a pair of (N
Mold '..., 414 is formed, humidity sensitive with electrode; Niko 5c1
Shi! Ta.

夷1tip Example 5 The Fe2O and LiNbU shown to the first person are shown in the table 7
The ratio of the attack to the mole is 1 (■shi, Hlf j:L:
In the same way as in the case of 'I' No. iii, a disk-shaped k (family) was created, and f1'' was added to +270'C.
:'J Heat radiation for 20 minutes)jT! , and create a burnt red body, and then 1' IIQ + High' mold 44 (busy i =
' = completed, electric 1 damage A' moisture sensing element was installed.

Evening /71I11ri1''6 Nozohi 7$ Jshit':
,l? ',? (2y+< sfc F e, u,
, ]v, b20. Bt-hi Li.

11.11r of morchi made with C"03 as batter, and wood 1'
) l', 4L, powder borrowed, NJ-sha. This 1'1 tree 0''
The fixture was molded at a pressure of approximately 200 K9/II.

lfk pressure molded sample at a temperature set at 700°C for about 2
Did you bake it for an hour? , >: K c+ crushed.

The pulverized product was pressure-molded, re-fired at 700°C, and pulverized again. A sintered body was prepared using the ground material as a powder mixture in the same manner as in the above example, and a 1 mel comb-shaped electrode was formed to obtain a moisture-sensitive element. .

Comparative Example 2 Fe20. and Li1VbO, were punched at the molar ratio shown in the table, a disk-shaped sample was prepared in the same manner as in the example described above, and the sample was heat-treated at a temperature of 1000°C for 6 hours to obtain a sintered body. A moisture-sensitive element with an IL canopy was obtained by forming a pair of cathedral gold electrodes.

Using the humidity sensitive circuit obtained in the above Examples and Comparative Examples, the characteristics of the relative humidity versus the electric wind turbine value were calculated,
Resistance value u<r) at 25°C and 40% relative resistance and 25
The resistance values (l<t) at 80% relative humidity and the composition are shown in Table 1.

The difference is that the obtained moisture-sensitive element has a diffraction intensity of 1 (1+l) and a diffraction angle of 2θ = 24.2° for X-ray diffraction using alpha rays on the Cu-R turn. Diffraction robbery (
The strong 1 current ratio '+/'t with 12) is also shown in Table 21'1.

Incidentally, the attached Figure 1 shows the X-ray cycle of the moisture-sensitive element C'76-person αF-d, which was marked f4 in Example 4. Turn diagram 1
kfi, su.

Furthermore, in &;S+1 Fig. 2, Example 3 (curve b),
Example 4 (curve d), implementation drift (+Il,'
: c) and Comparative Example 2 (curve a) 1 declined/i
￥-Wet element's 41-Kari [(Moe) adhesive vs. electrical resistance 1J" value (
The characteristic curve of logarithm) is shown.

\

[Brief explanation of the drawing]

Figure 1 shows C' of the moisture-sensitive element obtained in j:
FIG. 2 shows the relative humidity versus electricity of the humidity sensing elements obtained in Example 3, Example 4, Example 7, and Comparative Example 2. It is a graph showing a characteristic curve of resistance value (logarithm). Fig. 1 CuK father 2θ Brush 2 Fig. Ne U vs. 3X degrees (', 4)

Claims (1)

[Claims] 1. Salt containing iron, niobium and lithium as metal components 1.
-ru≦The deer of the genus oxide consists of 71 bodies and 1Lc'
Entering piece 1 dansen and 〼゛non times by u-λα ray (〕1
Angle 2θ = 29, bo ±0, 2 - Kotake 1 Iupita l: 1° A] Moisture sensitive ≠ child. 2. Xl & 9 [!, IJ 4A by C”u-Aα ray
□The diffraction value IB-(+1) of the lean angle 2θ-29,5° to 02° and the diffraction value IB-(+1) of the diffraction angle 2θ-242°
Strong suction ratio with 1 strength mouth, )' I/l! is 0.05~
0.7'tThe moisture sensing element according to claim 1.