CN1004739B - Humidity sensor and the method of making - Google Patents
Humidity sensor and the method of making Download PDFInfo
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- CN1004739B CN1004739B CN85104273.2A CN85104273A CN1004739B CN 1004739 B CN1004739 B CN 1004739B CN 85104273 A CN85104273 A CN 85104273A CN 1004739 B CN1004739 B CN 1004739B
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- humidity
- sensitive element
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- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 38
- 229920002521 macromolecule Polymers 0.000 claims abstract description 14
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 12
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 25
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
- -1 amine compound Chemical class 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 claims description 3
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001124 trientine Drugs 0.000 claims description 3
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 2
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract 3
- 230000004043 responsiveness Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 7
- 229910052737 gold Inorganic materials 0.000 description 7
- 239000010931 gold Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical class CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007791 dehumidification Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002547 anomalous effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003865 secondary ammonium salts Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
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Abstract
The present invention relates to a humidity sensitive element and a manufacture method thereof. The humidity sensitive element of the present invention is provided with a plasma polymerization macromolecule layer of hydrophobic organic compounds between a pair of electrodes or on at least one electrode. The macromolecule layer with amino groups is attached on the plasma polymerization macromolecule layer, and the macromolecule layer with amino groups is composed of amino groups and introduced ammonium salt type hydrophilic groups. The humidity sensitive element of the present invention has the effects of good responsibility and good durability.
Description
This invention relates to humidity-sensitive element and autofrettage thereof.What more particularly, relate to is applied humidity-sensitive element in aspect and the autofrettages of measuring in various industrial process gas and the recyclegas thereof such as moisture content, the moisture content in the mensuration gas cylinder gas and common hygroscopy.
In the past, as wet sensory material, it is formed humidity-sensitive film with polyelectrolyte on the solid substrate that various humidity-sensitive elements such as insulator, piezoelectrics, semiconductor are used, this humidity-sensitive element has been known.
Wherein, with piezoelectrics, it particularly is the humidity-sensitive element of substrate with piezoelectric elements such as quartz vibrators, because the hygroscopic effect of humidity-sensitive film changes whole weight, the oscillation frequency of piezoelectric element also changes and measures amount of moisture as index thus, with corresponding another kind of mode, promptly compare with the resistance of humidity-sensitive film itself and the mode that is changed to index of electrostatic capacitance, it can measure the amount of moisture of low concentration, the amount of moisture of parts per million (ppm) order of magnitude particularly, and make such piezoelectric type humidity-sensitive element, usually, be on piezoelectric element, to form pair of electrodes, apply various polyelectrolytes on it.
Yet, such humidity-sensitive element, because humidity-sensitive film is to apply to form, abundant inadequately with the stickability of electrode surface, make the poor durability of humidity-sensitive film, and when measuring a few percent order of magnitude micro-moisture, sensitivity and stability are also good inadequately, also exist the unmanageable problem of the thickness of humidity-sensitive film own.
Equally, between the pair of electrodes on insulator and the semiconductor, form polyelectrolyte membrane as humidity-sensitive film, in such resistance-type or capacitive moisture sensor.The permanance of film, response speed, stability etc. all exist same problem.
At these problems, the present inventor had once adopted the plasma polymerization macromolecule membrane of its top layer introducing hydrophilic group as humidity-sensitive film, had obtained to eliminate the piezoelectric type humidity-sensitive element (spy opens clear 59-24234 communique) of the problems referred to above.
The above-mentioned knowledge of the present invention expansion and obtaining, its objective is provides the humidity-sensitive film that possesses based on the plasma polymerization polymeric membrane, has further improved permanance and has improved the humidity-sensitive element of responsiveness.
According to the present invention, the humidity-sensitive element that is provided, it is characterized in that, form in the humidity-sensitive element of humidity-sensitive film between humidity-sensitive element is with the pair of electrodes on the solid substrate or at least one electrode, the basic structure of above-mentioned humidity-sensitive film is, form interior layer by hydrophobic organic compound plasma polymerization macromolecule layer, form by the plasma polymerization of organic amine compound on it and contain the superficial layer that amino macromolecule layer is formed, and in containing in the amino macromolecule layer of above-mentioned superficial layer, conversion amino is introduced ammonium salt type hydrophilic radical.
And, the manufacture method of the above-mentioned humidity-sensitive element of optimum is provided.
Description of drawings:
Fig. 1 and Fig. 2 are the front view and the side views of humidity-sensitive element example of the present invention, and Fig. 3 is the key diagram of same structure.Fig. 4 is the key diagram of expression humidity-sensitive element manufacturing process of the present invention, Fig. 5 and Fig. 6 are respectively the curve maps that the humidity responsiveness of expression humidity-sensitive element of the present invention is removed comparative example, Fig. 7 is that expression is with comparative example equally, the curve map of permanance is shown, Fig. 8 is illustrated in the scatter chart of the interior nitrogen atom content of humidity-sensitive film superficial layer of humidity-sensitive element of the present invention along thickness direction, and Fig. 9 has represented to use the responsiveness curve of the humidity-sensitive element of the present invention of various organic amine compounds.
(1) ... humidity-sensitive element, (2) ... quartz vibrator, (3) (3 ') ... humidity-sensitive film, (3a) (3 ' a) ... plasma polymerization polyphenyl ethamine, (3b) (3 ' b) ... plasma polymerization polymeric membrane, (4) (4 ') of containing ammonium salt type hydrophilic group ... gold electrode.
The most outstanding characteristics of the present invention are, the structure of humidity-sensitive film, interior layer is essentially hydrophobic, superficial layer has the hydrophilic radical of ammonium salt type, no matter and that layer, all be the macromolecule layer that constitutes by plasma polymerization.
The interior layer of humidity-sensitive film of the present invention be humidity-sensitive element with solid substrate on, form after the pair of electrodes, under the steam of hydrophobic organic compound, add the plasma polymerization condition and form.As the hydrophobic organic compound of usefulness at this moment, can have various not with the organic compound of hydrophilic radical, for example, unsaturated hydrocarbon such as aromatic series such as vinyl aromatic compound such as styrene, divinylbenzene and benzene, toluene and ethene, propylene, also available two or more.Can also form sandwich construction.Wherein be advisable to use styrene to carry out plasma polymerization.There is no particular limitation for the polymerizing condition of plasma, usually, in the steam of the above-mentioned hydrophobic organic compound of 0.1-2 holder, adopts 0.1～100KH
ZThe glow discharge condition be advisable.
The thickness of the interior layer of Xing Chenging is advisable with 0.01～10 μ m usually like this.Adjust the time of above-mentioned plasma polymerization, can easily control this thickness.The plasma polymerization polymeric membrane that constitutes this interior layer itself just has higher degree of crosslinking, and adherends such as electrode solid substrate are had firm cohesive, and has constituted substantial hydrophobicity rete by the condensate of hydrophobic organic compound.Thereby basal layer as humidity-sensitive film of the present invention.
Make the superficial layer of humidity-sensitive film of the present invention, be to form the solid substrate of above-mentioned interior layer, under the organic amine compound steam, add the plasma polymerization condition, on this interior layer, form earlier and contain amino macromolecule membranous layer, again through chemical treatment, replace the amino that contains in the amino macromolecule membranous layer by the hydrophilic group of ammonium salt type thereafter.As the organic amine compound in this situation, can enumerate and have substituent amine of straight chain shape at least as diallylamine, diamylamine, diethyl allylamine, N, N, N ', N '-tetramethylethylenediamines etc., and ring-type or aromatic amine such as aniline, pyridine, phenyl ethylamine can be enumerated triethylamine, ethylenediamine, diethylene triamine, trien etc. in addition.Also it can be used in combination more than two kinds.Wherein so that be advisable with tertiary amines such as having substituent tetramethylethylenediamine of straight chain shape and diethyl allylamine.The plasma polymerization condition with under the steam of 0.0～2 organic amine compound that holds in the palm, adopts 0.1～100KH usually
ZDischarging condition be advisable.The thickness of superficial layer is advisable with 0.01～10 μ m, and this can utilize the time of above-mentioned plasma polymerization, and adjustment contains amino polymeric membrane layer thickness and controlled.
The polymeric membrane that plasma polymerization by organic amine compound forms on above-mentioned interior layer, it is the polymeric membrane that contains amino high-crosslinking-degree, and generate free radical when also on the hydrophobic polymer film of interior layer, relying on glow discharge and carry out chemical bond, form integrated film.The amino that the monomer organic amine compound is had differs behind plasma polymerization and establishes a capital in the chain that remains in polymeric membrane.Promptly as previously mentioned, under the plasma polymerization condition of organic amine compound, owing to generate many free radicals and ion, the random polymerization crosslinking reaction between carbochain (sub stituent) will be occupied an leading position, and in addition, amino reactions such as decomposition also will take place.About this point, present inventors have also obtained interesting knowledge, promptly at the plasma polymerization of above-mentioned organic amine compound and polymeric membrane in, amino amount is in the majority in its face side, the face side occupies few within it.Such gradient type amino content, the occasion that particularly has the substituent organic amine compound of above-mentioned straight chain shape in use, particularly remarkable, can believe that this gradient is the response with humidity-sensitive element of the present invention, particularly with the rapid suction of moisture to be taken off effect closely related.
Contain chemical treatment amino in the amino polymeric membrane to be advisable in the steam that remains on halogenated alkyl to above-mentioned.At this moment the halogenated alkyl of usefulness selects for use a halogenated lower alkyl comparatively suitable, and its object lesson has methyl chloride, tonsilon, iodate methyl, Diethylaminoethyl etc.Be present in the amino that contains in the amino polymeric membrane, contact, just will be transformed to ammonium salt type hydrophilic groups such as committee's ammonium salt, tertiary amine salt, secondary ammonium salt by alkylation with this halogenated alkyl steam.This contact is carried out under heating, and carries out to promote reaction, also can carry out under the normal temperature.Preferably adjust the halogenated alkyl steam,, contact with the formed humidity-sensitive element that contains amino polymeric membrane with flow about 1 liter/minute under the normal pressure.Also can keep suitable duration of contact, be advisable with 30～300 minutes usually according to the superficial layer film thickness.
By above-mentioned interior layer constitute humidity-sensitive film with superficial layer and the used solid substrate of humidity-sensitive element made to be the detection mode that adopts with plan selected.For example, when the preparation making was the humidity-sensitive element of index with resistance and changes in capacitance, above-mentioned solid substrate adopted insulator and semiconductor, on its one side pair of electrodes was set, particularly comb-type electrode, the humidity-sensitive film of this interelectrode each electrode of formation covering then.The optimum structure of humidity-sensitive element of the present invention is the piezoelectric type humidity-sensitive element, its solid substrate adopts piezoelectrics, form electrode respectively on its two sides, at least on its one side, form humidity-sensitive film, this humidity-sensitive element combines with its mensuration mode, can be stably and measure moisture parts per million (ppm), extremely low concentration for a long time.As at this moment piezoelectrics quartz vibrator, calcium carbide, Rochelle salt, barium titanate crystallization, zincite crystal etc. are arranged, especially with the tabular quartz vibrator for well.In addition, the electrode that forms on solid substrate can adopt precious metal films such as gold, silver.This can be formed by evaporation.
Owing to humidity-sensitive film that humidity-sensitive element of the present invention possessed, be to be on the plasma polymerization polymeric membrane (interior layer) of sulphur water-based in aforesaid essence, be integrally formed the plasma polymerization polymeric membrane (superficial layer) of introducing ammonium salt type hydrophilic group, thereby only advance moisture absorption and dehumidification at superficial layer, and inside does not absorb moisture content in fact, and moisture is not shifted to inside yet.And, because it is the highest that the hydrophilic group that superficial layer is introduced is positioned at its concentration of surface of this superficial layer, reduce gradually inside, so no matter be that moisture absorption or dehumidification can both carry out smoothly, the harmful effect of the slow grade of the response that causes because of residual moisture in the humidity-sensitive film is limit extremely in Min..Thereby the responsiveness of humidity-sensitive element of the present invention and stable fine.As sensitive element, its permanance also is improved.
Embodiment 1: at thickness is that 0.2mm, diameter are the two sides middle body of the disk shape quartz vibrator (2) of 14mm, evaporation and form the gold electrode that diameter is 8mm (thickness is about 1 μ m).The oscillation frequency of this oscillator is about 9.03MH
Z
Above-mentioned oscillator (2) is placed in the plasma polymerization.The plasma polymerization structure of this moment is shown in Fig. 4, among the figure, (7) be that aluminium matter discharge electrode, (8) are that compound ejiction opening, (10) are that high frequency electric source, (11) are that the connecting pipe that leads to vacuum pump, container, (12B) that (12A) is the hydrophobic organic compound styrene monomer are organic amine compound N for same a pair of discharge electrode, (9), N, N ', the container of N '-tetramethylethylenediamine, (13) are that sealing gasket, (14) are airtight containers.In order to cover the garden shape gold electrode surfaces that adheres to oscillator (2), be the plasma polymerization film of 12mm to form diameter, so shelter around it with aluminum pressing plate (7 ').
Then, by vacuum pump above-mentioned airtight container (14) is reduced pressure, reduce to below 0.01 torr, charge into the styrene monomer steam again, till reaching 1 torr, carry out the plasma polymerization in 20 seconds under the following conditions, then adhere to the formation plasticon respectively at the two sides of gold electrode middle body, its thickness is about 3000A.
(discharging condition)
Temperature: 25 ℃
Discharge frequency: 1KH
Z
Discharge power: 3.5W
And then, charge into N with being decompressed to 0.01 holder in the airtight container, and N, N ', N '-tetramethyl diethylamine steam until 1 torr, under above-mentioned same condition, carries out the plasma polymerization in 60 seconds, has then formed thickness and be about 3000 on plasticon
, contain amino polymeric membrane.
With what make like this, the quartz vibrator that has formed the plasma polymerization film was placed in the methyl chloride steam groove (charge into 100% methyl chloride gas) after 12 hours in the airtight container of normal pressure, the amino that contains in the amino polymeric membrane (superficial layer) is changed to alkyl, is replaced by ammonium salt type hydrophilic group.
The humidity-sensitive element of the present invention that makes like this is shown among Fig. 1 to Fig. 3.Humidity-sensitive element among the figure (1) is to adhere to form gold electrode (4) (4 ') on the two sides of quartz vibrator (2), adheres to the humidity-sensitive film (3) (3 ') that shape is covered in this electrode again.End at gold electrode (4) (4 ') is connected with lead-in wire (6) (6 ') by joint (5) (5 '), and during use, this lead-in wire is connected to signal processing circuit.Humidity-sensitive film (3) (3 ') be by the plasma polymerization polystyrene film (3a) (3a ') of close attachment on electrode and oscillator and thereon close attachment plasma polymerization polymeric membrane (3b) (3b ') that form, that contain ammonium salt type hydrophilic group constitute.In use, place these humidity-sensitive films (3) (3 '), it is exposed in the tested gas,, just can carry out the mensuration of moisture according to the frequency change of quartz vibrator at this moment.
The humidity-sensitive element that makes like this is fixed in the container with test portion gas inlet tube and escape hole, has carried out hygroscopy.Its result provides as follows with comparative example.
(1) for N
2Middle moisture concentration is the responsiveness of 500～10000ppm.The N that will contain 10000ppm moisture
2Gas fed in the said vesse 10 minutes, according to absorption to moisture, and the output of instrumentation humidity-sensitive element, and then feed the N of the moisture 500ppm of being divided into
2Gas is measured the variation of its output, thereby estimates responsiveness.It the results are shown in Fig. 5.Among the figure, (A) be the output change curve of humidity-sensitive element of the present invention, (B) be the output change curve that has with the existing humidity-sensitive element of spline structure, but its plasma polymerization polystyrene individual layer of no use does not have at the sulfonation base of this polystyrene film top layer introducing as hydrophilic group as the humidity-sensitive film basis yet.
Like this, in than higher concentration range, for humidity by 10000ppm to the rapid variation of 500ppm, humidity-sensitive element of the present invention (A) is decided state with reaching weighing apparatus in about 0.5 hour, with original humidity-sensitive element (B; Reached weighing apparatus in about 4 hours and decide state) to compare, responsiveness is splendid.
(2) for moisture concentration be responsiveness and the aforementioned same way of 0～5ppm, (0 → 5 → 0ppm), mensuration output changes, and estimates its response in corresponding humidity variation in the extremely low concentration zone.It the results are shown among Fig. 6.
Like this, change for the humidity in the extremely low concentration zone, the particularly variation of moisture concentration minimizing, humidity-sensitive element of the present invention (A) is compared with original humidity-sensitive element, also draws the fabulous conclusion of responsiveness.
(3) permanance of humidity-sensitive film
Long-time continuous ground is measured and is contained the N that moisture is 1000ppm
2Gas, comprehensively it exports situation of change, estimates the permanance of humidity-sensitive film.It the results are shown in Fig. 7.Here, it is very big that original humidity-sensitive element (B) initial stage sensitivity descends, and (among the figure, dotted portion) is membranous after 90 days that variation has taken place, and that humidity-sensitive element initial stage sensitivity of the present invention descends is very little, even through also not finding the ANOMALOUS VARIATIONS of film in 120 days.
For except using the iodate methyl as the halogenated alkyl, formed the humidity-sensitive film of double membrane structure similarly to Example 1, with except using aniline to replace N, N, N ', N '-tetramethylethylenediamine and with the iodate methyl as outside the halogenated alkyl, formed the humidity-sensitive film of double membrane structure similarly to Example 1, use the ESCA(electron spectroscopy for chemical analysis) and the Ar(aryl) etch, the distribution of ammonium content in the superficial layer is measured.The analysis condition of its ESCA is as follows:
X-ray source: 9KV, 30mA, magnesium target
Sweep velocity: 1ev/ second and 0.1ev/ second
The Ar(aryl) etch: 2KV, 20mA
Based on this measurement result, be N with thickness
1SThe relation of peak strength is shown in Fig. 8.
Like this, compare with the situation of monomer as superficial layer such as aromatic amines such as aniline with use.Distinguished that use such as tetramethylethylenediamine etc. has the substituent surface film of straight chain shape, the gradient from the surface to inner ammonium content is very big, and ammonium is maximum in surface, has good rapid moisture absorption dehumidification.
Use various amines (triethylamine, ethylenediamine, diethylene triamine, trien, diallylamine) respectively as organic amine compound, make piezoelectric type humidity-sensitive element similarly to Example 1, measured the responsiveness of each humidity-sensitive element to moisture, base the results are shown among Fig. 9.
As mentioned above, compare with the humidity-sensitive element that with individual layer plasma polymerization polymeric membrane is humidity-sensitive film, humidity-sensitive element of the present invention all has good effect aspect responsiveness and the permanance.Particularly, even compare with the humidity-sensitive element of original coated membranous type, its responsiveness and permanance also are good, and the control of thickness is easy, and product quality management is easy, and owing to be under dry conditions, to make generally, direct commodity in use oxidizing gases, so it is easy to have manufacturing process, lossless, economic dispatch advantage.
Claims (10)
1, at the humidity-sensitive element that forms humidity-sensitive film on the solid substrate that humidity-sensitive element is used between pair of electrodes or at least one electrode.
It is characterized by, the basic structure of above-mentioned humidity-sensitive film is, form interior layer and form thereon by the plasma polymerization macromolecule layer of hydrophobic organic compound and contain amino macromolecule layer and form superficial layer by the plasma polymerization of organic amine compound, and contain in the amino macromolecule layer at above-mentioned superficial layer, introduce ammonium salt type hydrophilic group substituted-amino.
2, humidity-sensitive element according to claim 1, wherein the water diversion of ammonium salt type hydrophilic group has Gradient distribution along thickness direction, becomes in the face side amount of superficial layer greatly, reduces in the interior layer side.
3, humidity-sensitive element according to claim 1, wherein the solid substrate used of humidity-sensitive element is piezoelectrics.
4, the autofrettage of humidity-sensitive element, it is characterized by, evaporation forms pair of electrodes on the solid substrate that humidity-sensitive element is used, it is placed the steam of hydrophobic organic compound, carry out plasma polymerization, forming polymeric membrane between its electrode or at least one electrode, then under the steam of organic amine compound, carry out plasma polymerization, after forming the polymeric membrane that contains amino on the above-mentioned polymeric membrane, remain on again in the halogenated alkyl steam, the above-mentioned amino that contains in the amino polymeric membrane is transformed into ammonium salt type hydrophilic group.
5, autofrettage according to claim 4, wherein used organic amine compound can be from diallylamine, diethyl allylamine, N, N, N ' selects in N '-tetramethylethylenediamine, aniline, pyridine, phenyl ethylamine, triethylamine, ethylenediamine, diethylene triamine and the trien.
6, autofrettage according to claim 4, wherein used halogenated alkyl can be selected from methyl chloride, tonsilon, iodate methyl and Diethylaminoethyl.
7, autofrettage according to claim 4, wherein used hydrophobic organic compound are vinyl aromatic compounds.
8, autofrettage according to claim 4, the plasma polymerization of wherein said hydrophobic organic compound and organic amine compound is under high vacuum, carries out under the glow discharge condition of 0.1～100KHZ.
9, autofrettage according to claim 4, the solid substrate that wherein used humidity-sensitive element is used are piezoelectrics.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104273.2A CN1004739B (en) | 1985-06-05 | 1985-06-05 | Humidity sensor and the method of making |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85104273.2A CN1004739B (en) | 1985-06-05 | 1985-06-05 | Humidity sensor and the method of making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104273A CN85104273A (en) | 1986-12-03 |
| CN1004739B true CN1004739B (en) | 1989-07-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85104273.2A Expired CN1004739B (en) | 1985-06-05 | 1985-06-05 | Humidity sensor and the method of making |
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| Country | Link |
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| CN (1) | CN1004739B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6873638B2 (en) * | 2016-09-23 | 2021-05-19 | 太陽誘電株式会社 | Gas sensor and gas detection method |
| CN107014866A (en) * | 2016-12-20 | 2017-08-04 | 江苏常州酞青新材料科技有限公司 | A kind of lithium chloride dew cell manufacture craft |
| CN107884451B (en) * | 2017-11-07 | 2020-07-14 | 中创新海(天津)认证服务有限公司 | Device capable of rapidly and accurately detecting environment humidity |
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1985
- 1985-06-05 CN CN85104273.2A patent/CN1004739B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN85104273A (en) | 1986-12-03 |
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