JPS63257201A - Humidity-sensitive resistor - Google Patents
Humidity-sensitive resistorInfo
- Publication number
- JPS63257201A JPS63257201A JP62090935A JP9093587A JPS63257201A JP S63257201 A JPS63257201 A JP S63257201A JP 62090935 A JP62090935 A JP 62090935A JP 9093587 A JP9093587 A JP 9093587A JP S63257201 A JPS63257201 A JP S63257201A
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- sensitive resistor
- fap
- calcium
- moisture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001768 cations Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 229910052587 fluorapatite Inorganic materials 0.000 claims description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical group [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 4
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 4
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229940077441 fluorapatite Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 description 1
- 101100283604 Caenorhabditis elegans pigk-1 gene Proteins 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 1
- 229940043256 calcium pyrophosphate Drugs 0.000 description 1
- NBTASZQYZYVJAU-UHFFFAOYSA-L calcium;fluoro-dioxido-oxo-$l^{5}-phosphane;dihydrate Chemical compound O.O.[Ca+2].[O-]P([O-])(F)=O NBTASZQYZYVJAU-UHFFFAOYSA-L 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Non-Adjustable Resistors (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［産業上の利用分野］
この発明は感湿抵抗体に係り、特には、アパタイト系焼
結体からなる感湿抵抗体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a humidity-sensitive resistor, and particularly to a humidity-sensitive resistor made of an apatite-based sintered body.
［従来の技術〕
感湿抵抗体は、雰囲気の相対湿度に対応した抵抗値を示
すものである。このような感湿抵抗体として、水酸アパ
タイトの焼結体が知られている（特開昭５９−６０３４
８号公報、特開昭５９−６０３５０号公報参照）。[Prior Art] A humidity-sensitive resistor exhibits a resistance value corresponding to the relative humidity of the atmosphere. As such a moisture-sensitive resistor, a sintered body of hydroxyapatite is known (Japanese Patent Laid-Open No. 59-6034).
8 and Japanese Patent Application Laid-Open No. 59-60350).
［発明が解決しようとする問題点］
しかしながら、水酸アパタイト焼結体は、湿度に対応す
る抵抗値自体が高いので、感度が良好でなく、特に、低
湿度側での湿度測定に問題がある。[Problems to be solved by the invention] However, since the hydroxyapatite sintered body itself has a high resistance value corresponding to humidity, the sensitivity is not good, and there is a problem in humidity measurement, especially at low humidity. .
また、低湿度側から高湿度側への湿度測定と、高湿度側
から低湿度側への湿度測定とにおける抵抗値にヒステリ
シスが生じ、信頼性が欠けるという難点を有していた。In addition, hysteresis occurs in the resistance value when measuring humidity from the low humidity side to the high humidity side and from the high humidity side to the low humidity side, resulting in a drawback of lack of reliability.
したがって、この発明の目的は、湿度に対応する抵抗値
が充分に低く、しかもヒステリシスの問題も殆どない感
湿抵抗体を提供することにある。Therefore, an object of the present invention is to provide a humidity-sensitive resistor which has a sufficiently low resistance value corresponding to humidity and which has almost no problem of hysteresis.
［問題点を解決するための手段］
上記問題点を解決するために、この発明では、感湿抵抗
体としてフッ素アパタイトの焼結体を用いている、この
フッ素アパタイトのカルシウムイオンの一部をイオン半
径が０．９５Ａを越え１．３５Ａ未満である陽イオンの
一種または２種以上で置換すると、抵抗値がさらに低下
し、低湿度側における湿度測定に特に有利となる。[Means for Solving the Problems] In order to solve the above problems, in the present invention, a sintered body of fluoroapatite is used as a moisture-sensitive resistor, and some of the calcium ions of this fluoroapatite are ionized. When replaced with one or more cations having a radius of more than 0.95 A and less than 1.35 A, the resistance value further decreases, which is particularly advantageous for humidity measurement on the low humidity side.
［実施例］
以下、添付の図面を参照してこの発明をさらに詳しく説
明する。[Example] Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.
第１図は、この発明の感湿抵抗体を有する湿度素子１０
の断面図である。この湿度素子ｌＯは、フッ素アバタイ
’ｐ （ＦＡｐ）の焼結体からなる感湿抵抗体１１を備
え、感湿抵抗体１１の両面に電極１２および１３が形成
されている。電極１２および１３は、抵抗測定素子１４
にそれぞれ接続されており、雰囲気の相対湿度に対応す
る抵抗値が抵抗素子１４によって測定され、湿度を知る
ことができる。FIG. 1 shows a humidity element 10 having a humidity sensitive resistor of the present invention.
FIG. This humidity element 10 includes a humidity sensitive resistor 11 made of a sintered body of fluorine abatai'p (FAp), and electrodes 12 and 13 are formed on both sides of the humidity sensitive resistor 11. Electrodes 12 and 13 are connected to resistance measuring element 14
The resistance value corresponding to the relative humidity of the atmosphere is measured by the resistance element 14, and the humidity can be determined.
この発明の感湿抵抗体を形成するＦＡＰは、式Ｃａ、。The FAP forming the moisture sensitive resistor of this invention has the formula Ca.
（ＰＯ２）６Ｆ２．で示されるものであるが、そのカル
シウムイオンの一部をイオン半径が０．９５Ａを越え１
．３５Ａ未満である陽イオンの一種または２種以上で置
換しカルサイト型構造とすると抵抗値がさらに低下し、
特に低湿度側での湿度測定にイ］利となる。置換陽イオ
ンとしては、１価陽イオン（例えば、リチウム、ナトリ
ウム、カリウム、ｆｉ４）、２価の陽イオン（例えば、
バリウム、ストロンチウム、マグネシウム）、および３
価の陽イオン（例えば、ランタン、ユーロピウム、ビス
マス）がある。(PO2)6F2. However, if some of the calcium ions have an ionic radius exceeding 0.95A, 1
．． When substituted with one or more cations less than 35A to create a calcite structure, the resistance value further decreases,
This is particularly useful for humidity measurements on the low humidity side. Substitution cations include monovalent cations (for example, lithium, sodium, potassium, fi4), divalent cations (for example,
barium, strontium, magnesium), and 3
There are valent cations (e.g. lanthanum, europium, bismuth).
ところで、ＦＡｐの合成方法としては、大別して、乾式
法と湿式法とが知られている。乾式法は、ＦＡＰの原料
（リン酸カルシウムとフッ化カルシウム、ピロリン酸カ
ルシウムとフッ化カルシウム等）を数百℃もの高温で焼
成する工程を含むため、フッ素が揮散しやすく、均一な
組成を有するＦＡｐ粉末を得ることが困難である。By the way, methods for synthesizing FAp are broadly classified into dry methods and wet methods. The dry method involves firing the raw materials for FAP (calcium phosphate and calcium fluoride, calcium pyrophosphate and calcium fluoride, etc.) at a high temperature of several hundred degrees Celsius, so fluorine is easily volatilized and FAp powder with a uniform composition can be produced. difficult to obtain.
湿式法としては、リン酸一水素カルシウムの懸濁液にフ
ッ化カルシウムを加えて両者を反応させる方法、モノフ
ルオロリン酸カルシウム二水塩を加水分解する方法等が
知られている。しかしながら、これらの方法は副生物を
伴なうことが多く、純粋なＦＡｐが得られない、また、
湿式法によりで水酸アパタイトを製造する際にフッ素イ
オンを共存させてＦＡＰを合成することも知られている
が、得られたＦＡｐは非晶質である。Known wet methods include a method in which calcium fluoride is added to a suspension of calcium monohydrogen phosphate and the two are reacted, and a method in which calcium monofluorophosphate dihydrate is hydrolyzed. However, these methods often involve by-products, do not yield pure FAp, and
It is also known to synthesize FAP by coexisting fluorine ions when producing hydroxyapatite by a wet method, but the obtained FAp is amorphous.
ところで、ＦＡｐを感湿抵抗体に適用する際に、ＦＡｐ
粉末を焼結する必要があるが、一般に、焼結温度が高温
であればある程、ＦＡｐは、フッ素の揮発性によって大
気中の水分と反応してフッ素−水酸基固溶アパタイトに
変換することが知られている。感湿抵抗体としてみた場
合、フ素アパタイトに比較して、水酸アパタイトは抵抗
値が対数で１桁高くなるので、このような水酸基の導入
は、特に低湿度における湿度の測定に不利となる。した
がって、できるだけ低温で焼結できるＦＡｐが望まれて
いるが、従来の方法で得られたＦＡｐは、その点におい
て満足できるものではない。By the way, when applying FAp to a moisture-sensitive resistor, FAp
It is necessary to sinter the powder, but in general, the higher the sintering temperature, the more likely it is that FAp will react with atmospheric moisture due to the volatility of fluorine and convert into fluorine-hydroxyl solid solution apatite. Are known. When viewed as a moisture-sensitive resistor, hydroxyapatite has a logarithmically higher resistance value by an order of magnitude compared to fluoroapatite, so the introduction of such hydroxyl groups is disadvantageous, especially in measuring humidity at low humidity. . Therefore, FAp that can be sintered at as low a temperature as possible is desired, but FAp obtained by conventional methods is not satisfactory in this respect.
本発明者らは、上記従来法の欠点を解決する方法として
、ＦＡｐの原料として、リン酸一水素カルシウム（Ｃａ
ＨＰＯ４） 、炭酸カルシウム（ＣａＣＯ３）およびフ
ッ化カルシウム（ＣａＦｚ）を用いる湿式法を開発した
。すなわち、これら原料を所定の割合（すなわち、モル
比６：３：ｌ）で配合し、これをまずメカノケミカル作
用に供する。しかる後、これら原料を水中で反応（固体
−水系反応）させる。The present inventors have proposed using calcium monohydrogen phosphate (Ca
A wet method using HPO4), calcium carbonate (CaCO3) and calcium fluoride (CaFz) was developed. That is, these raw materials are blended in a predetermined ratio (ie, a molar ratio of 6:3:l), and this is first subjected to mechanochemical action. Thereafter, these raw materials are reacted in water (solid-water reaction).
メカノケミカル作用とは、固体物質が摩砕、摩擦、すベ
リ、切削、遠心、衝撃などの手段により加えられた機械
的エネルギーの一部を固体内部に保有することにより、
その物理化学的性状に変化をおこす作用を意味する（「
工業化学雑誌Ｊ７１巻、９号（１９８Ｂ） １３０１頁
）、このような作用は、上記原料をボールミルで混合粉
砕することによって容易に付与することができる。ボー
ルミルによる処理は、原料混合物に水を加え、常温でお
こなえばよい、粉砕時間は、通常、５時間ないし４８時
間である。Mechanochemical action is when a solid substance retains a part of the mechanical energy applied by means such as grinding, friction, sliding, cutting, centrifugation, impact, etc.
It means an action that causes a change in its physicochemical properties (“
Industrial Chemistry Magazine J71, No. 9 (198B, p. 1301), such an action can be easily imparted by mixing and pulverizing the above raw materials in a ball mill. The ball milling process can be carried out by adding water to the raw material mixture at room temperature, and the grinding time is usually 5 to 48 hours.
ついで、水中で上記原料を固体−水系反応させる。固体
−水系反応は、原料系と生成系との水中溶解度の差を用
いた反応であり、この発明においては、上記原料の溶解
度が生成物ＦＡｐの溶解度よりも大きいため、一旦生成
したＦＡｐはそのまま沈降し、反応の平衡は常に生成物
の方向に傾き、ＦＡｐの生成反応が進行する。この反応
時の温度は、１００℃以下、好ましくは８０℃ないし１
００℃である。この方法によれば、このように低い温度
で反応がおこなえるので、従来の乾式法のように反応中
にフッ素が揮散することによる組成の不均一性は生じな
い。反応時間は１通常、８時間ないし１２時間である。Then, the raw materials are subjected to a solid-water reaction in water. The solid-water reaction is a reaction that uses the difference in solubility in water between the raw material system and the product system. In this invention, since the solubility of the raw material is greater than the solubility of the product FAp, once the FAp is produced, it can be used as is. The reaction equilibrium always tilts toward the product, and the FAp production reaction progresses. The temperature during this reaction is 100°C or less, preferably 80°C to 1°C.
It is 00℃. According to this method, since the reaction can be carried out at such a low temperature, compositional non-uniformity due to fluorine volatilization during the reaction does not occur as in conventional dry methods. The reaction time is usually 8 to 12 hours.
この固体−水系反応は定量的であり、副生物はほとんど
生じない。This solid-water reaction is quantitative and produces almost no by-products.
反応終了後は、ろ過等の手段によりＦＡｐを回収し、乾
燥する。こうして得たＦＡｐは、粒径０．１ないし０．
４ｐｍの微細な粉末の形態にあり、結晶性も良好である
。また、この方法によって製造されたＦＡｐは焼結性が
良好で、７００℃ないし８００℃という低い温度で焼結
をおこなうことができる。この方法によって製造された
ＦＡｐの、従来のＦＡｐとの構造（結晶構造等）上の差
異は充分に解明されていないが、この方法によって製造
されたＦＡｐは特に優れた湿度−抵抗値特性を有するこ
とは明らかとなっている。After the reaction is completed, FAp is recovered by means such as filtration and dried. The thus obtained FAp has a particle size of 0.1 to 0.
It is in the form of a fine powder of 4 pm and has good crystallinity. Furthermore, the FAp produced by this method has good sinterability and can be sintered at a low temperature of 700°C to 800°C. Although the structural differences (crystal structure, etc.) between FAp produced by this method and conventional FAp are not fully elucidated, FAp produced by this method has particularly excellent humidity-resistance characteristics. That is clear.
なお、Ｊ：記陽イオンで置換されたフッ素アパタイトを
得るためには、上記フッ素アパタイト原料にさらに当該
陽イオンの供給源例えば炭酸塩を加えて、上記と同様に
処理、反応をおこなえばよい、陽イオンによるカルシウ
ムイオンの置換率は、０，１ないし２０原子％とするこ
とが好ましい。In addition, in order to obtain fluoroapatite substituted with the J: cation, a source of the cation, such as a carbonate, may be further added to the fluoroapatite raw material, and the treatment and reaction may be carried out in the same manner as above. The substitution rate of calcium ions by cations is preferably 0.1 to 20 atomic %.
実施例 １
（Ａ） リン酸一水素カルシウム、炭酸カルシウムおよ
びフッ化カルシウムをモル比６：３：ｌでＦＡＰの合成
量が５０グラムとなるように秤量し、ボールミル中で水
２００ミリリットルとともに８Ｏｒｐｍで２４時間混合
拳粉砕した。この原料混合物を水中において１００℃で
１０時間反応させ、ＦＡｐを得た。得られたＦＡＰは、
平均粒径０．２ＪＬｍの微細な粉末であった。このＦＡ
ｐのＸ線回折図を第２図に示す。Example 1 (A) Calcium monohydrogen phosphate, calcium carbonate, and calcium fluoride were weighed at a molar ratio of 6:3:l so that the amount of FAP synthesized would be 50 grams, and the mixture was mixed with 200 ml of water in a ball mill at 8 Orpm. Mixed and fist-milled for 24 hours. This raw material mixture was reacted in water at 100° C. for 10 hours to obtain FAp. The obtained FAP is
It was a fine powder with an average particle size of 0.2 JLm. This FA
The X-ray diffraction pattern of p is shown in FIG.
（Ｅ）上記（Ａ）で得たＦＡｐ粉末にポリビニルアルコ
ールを加え造粒した後、圧粉密度が１．５ｇ／’ｃｍ３
となるように、直径１８．１５ｍｍ、厚さ１．０ｍｍ
の大きさにプレス成形し、７８０℃で２時間焼結させた
ところ良好な焼結体を得た。この焼結体の両面にスクリ
ーン印刷により銀ペーストを塗布し、５３０℃で焼付け
て電極を形成して湿度素子を得た。(E) After adding polyvinyl alcohol to the FAp powder obtained in (A) above and granulating it, the compacted powder density is 1.5 g/'cm3
The diameter is 18.15mm and the thickness is 1.0mm.
A good sintered body was obtained by press molding to a size of 1 and sintering at 780°C for 2 hours. Silver paste was applied to both sides of this sintered body by screen printing and baked at 530°C to form electrodes to obtain a humidity element.
この湿度素子の感湿特性（抵抗値（Ｒ）の対数値と相対
湿度（ＲＨ）との関係）を第３図に示す（曲線ａ） ０
ｍ定条件は２５℃、ＩＫＨｚ、１■であった。なお、上
記ＦＡｐの代りに水酸アパタイトを用いて同条件で作製
した湿度素子の感湿特性を第３図中曲線すで示す、第３
図に示す結果から、この発明の方法によって得たＦＡｐ
は、水酸アパタイトと比較して、感湿抵抗体としての抵
抗値が非常に低いことがわかる。The humidity-sensitive characteristics (the relationship between the logarithm of the resistance value (R) and the relative humidity (RH)) of this humidity element are shown in Figure 3 (curve a).
The constant conditions were 25° C., IKHz, and 1 μm. Note that the curve 3 in FIG.
From the results shown in the figure, it can be seen that FAp obtained by the method of this invention
It can be seen that the resistance value as a moisture-sensitive resistor is very low compared to hydroxyapatite.
また、本実施例で得た湿度素子について、相対湿度（Ｒ
Ｈ）を３０％から９０％まで加湿した場合および９０％
から３０％まで除湿した場合における抵抗値（Ｒ（Ω）
）を測定した（測定条件：２５℃、ＩＫＨｚ、ＩＶ）。Furthermore, regarding the humidity element obtained in this example, relative humidity (R
H) when humidified from 30% to 90% and 90%
Resistance value (R (Ω) when dehumidifying from to 30%
) was measured (measurement conditions: 25°C, IKHz, IV).
測定結果を以下の表１および表２に示すとともに、ヒス
テリシス曲線として第４図に示す（第４図において、抵
抗値は対数表示である）。The measurement results are shown in Tables 1 and 2 below, and are shown in FIG. 4 as a hysteresis curve (in FIG. 4, the resistance values are expressed in logarithm).
表 １ （加湿過程）
表 ２（除湿過程）
以上の結果から、この発明の感湿抵抗体は、抵抗値のヒ
ステリシスが殆どないことがわかる。Table 1 (humidifying process) Table 2 (dehumidifying process) From the above results, it can be seen that the humidity sensitive resistor of the present invention has almost no hysteresis in resistance value.
実施例 ２
リン酸−カルシウム、炭酸カルシウム、フッ化カルシウ
ムおよびＪ￥酸カリウムをモル比で６：２：１：０．５
の割合で秤量した後、実施例１と同様の方法により湿度
素子を得た。この湿度素子の感湿特性を第５図に示す、
測定条件は２５℃、１ｋＨｚ、１ｖであった。この結果
かられかるように、フッ素アパタイトのカルシウムイオ
ンの一部を所定の陽イオンで置換したものは、相対湿度
に対応する抵抗値がさらに低下する。Example 2 Calcium phosphate, calcium carbonate, calcium fluoride and potassium J-acid in a molar ratio of 6:2:1:0.5
After weighing at a ratio of , a humidity element was obtained in the same manner as in Example 1. The humidity sensitive characteristics of this humidity element are shown in Figure 5.
The measurement conditions were 25° C., 1 kHz, and 1 V. As can be seen from this result, when some of the calcium ions in fluoroapatite are replaced with predetermined cations, the resistance value corresponding to relative humidity further decreases.
［発明の効果］
以上述べたように、この発明によれば、湿度に対応する
抵抗値が充分に低く、しかも抵抗値のヒステリシスが殆
どない感湿抵抗体が提供される。[Effects of the Invention] As described above, according to the present invention, a humidity-sensitive resistor is provided which has a sufficiently low resistance value corresponding to humidity and has almost no hysteresis in the resistance value.
第１図は、この発明の感湿抵抗体を有する湿度素子の断
面図、第２図は、この発明の感湿抵抗体として用いるＦ
ＡｐのＸ線回折図、第３図は、この発明の一実施例に係
る感湿抵抗体の感湿特性を比較例とともに示すグラフ図
、第４図は、この発明の感湿抵抗素子の抵抗値のヒステ
リシスを測定したグラフ図、および第５図は、この発明
の他の実施例に係る感湿抵抗体の感湿特性を示すグラフ
図。
１１・會・感湿抵抗体、１２．１３・・φ電極、１４・
・・抵抗測定素子
出願人代理人 井埋士（５８４７）鈴江武彦、第１図FIG. 1 is a cross-sectional view of a humidity element having a humidity-sensitive resistor of the present invention, and FIG. 2 is a cross-sectional view of a humidity element having a humidity-sensitive resistor of the present invention.
The X-ray diffraction diagram of Ap, FIG. 3 is a graph showing the humidity-sensitive characteristics of the humidity-sensitive resistor according to one embodiment of the present invention together with a comparative example, and FIG. 4 is the resistance of the humidity-sensitive resistor of the present invention. FIG. 5 is a graph showing the measurement of the hysteresis of the value, and FIG. 5 is a graph showing the humidity-sensitive characteristics of a humidity-sensitive resistor according to another embodiment of the present invention. 11. Moisture-sensitive resistor, 12.13..φ electrode, 14.
...Resistance measuring element applicant's representative: Ibuji (5847) Takehiko Suzue, Figure 1
Claims (3)
炭酸カルシウムおよびフッ化カルシウムを所定の割合で
配合し、メカノケミカル作用に供した後、水中で反応さ
せることによって得たものである特許請求の範囲第１項
記載の感湿抵抗体。(2) Fluorapatite is calcium monohydrogen phosphate,
The moisture-sensitive resistor according to claim 1, which is obtained by blending calcium carbonate and calcium fluoride in a predetermined ratio, subjecting it to a mechanochemical action, and then reacting it in water.
オン半径が０．９５Ａを越え１．３５Ａ未満である陽イ
オンの１種または２種以上で置換した特許請求の範囲第
２項記載の感湿抵抗体。(3) The moisture-sensitive resistor according to claim 2, wherein a part of the calcium ions of the fluoroapatite is replaced with one or more cations having an ionic radius of more than 0.95A and less than 1.35A. body.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62090935A JPH07118403B2 (en) | 1987-04-15 | 1987-04-15 | Moisture-sensitive resistor |
| US07/180,812 US4855118A (en) | 1987-04-15 | 1988-04-12 | Method of producing fluorapatite |
| US07/336,911 US4971739A (en) | 1987-04-15 | 1989-04-12 | Method of producing fluorapatite and a moisture sensitive resistor using fluorapatite obtained by the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62090935A JPH07118403B2 (en) | 1987-04-15 | 1987-04-15 | Moisture-sensitive resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63257201A true JPS63257201A (en) | 1988-10-25 |
| JPH07118403B2 JPH07118403B2 (en) | 1995-12-18 |
Family
ID=14012306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62090935A Expired - Lifetime JPH07118403B2 (en) | 1987-04-15 | 1987-04-15 | Moisture-sensitive resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118403B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025358A1 (en) * | 2004-08-31 | 2006-03-09 | Japan Science And Technology Agency | Detector for chemical sensor device and use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6014481A (en) * | 1983-07-05 | 1985-01-25 | Canon Inc | Luminescent device |
-
1987
- 1987-04-15 JP JP62090935A patent/JPH07118403B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6014481A (en) * | 1983-07-05 | 1985-01-25 | Canon Inc | Luminescent device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006025358A1 (en) * | 2004-08-31 | 2006-03-09 | Japan Science And Technology Agency | Detector for chemical sensor device and use thereof |
| JPWO2006025358A1 (en) * | 2004-08-31 | 2008-05-08 | 独立行政法人科学技術振興機構 | Detector for chemical sensor device and use thereof |
| JP4670084B2 (en) * | 2004-08-31 | 2011-04-13 | 独立行政法人科学技術振興機構 | Detector for chemical sensor device and use thereof |
| US8277750B2 (en) | 2004-08-31 | 2012-10-02 | Kinki University | Detector for chemical sensor device and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07118403B2 (en) | 1995-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4855118A (en) | Method of producing fluorapatite | |
| EP2838836B1 (en) | Method for producing li-ion conductive lithium aluminium titanium phosphates and use thereof as a solid-state electrolyte | |
| KR102662015B1 (en) | Boron nitride powder, method for producing boron nitride powder, and cosmetics | |
| JPH02296706A (en) | Amorphous or irregular- laminate and spherical in particular boron nitride and its production method | |
| DE10301061A1 (en) | Burnt alumina, process for its production and fine alpha alumina powder obtained by using the fired alumina | |
| KR20230169256A (en) | Hexagonal boron nitride powder for cosmetics, and cosmetics | |
| JPS63257201A (en) | Humidity-sensitive resistor | |
| US4322485A (en) | Preparation of materials | |
| JPH0524856B2 (en) | ||
| JP2021116205A (en) | Hexagonal boron nitride powder and method for producing the same, and cosmetics and method for producing the same | |
| EP0810189B1 (en) | Liquid phase sintering process for alumina ceramics | |
| US3804765A (en) | Adjusting ferroelectric ceramic characteristics during formation thereof | |
| US20240277586A1 (en) | Hexagonal boron nitride powder and method for producing same, and cosmetic preparation and method for producing same | |
| GB2052462A (en) | Improvements in or relating to the preparation of ion conductors | |
| JPS585844B2 (en) | Stable β-type alumina slurry | |
| US6117595A (en) | High sodium ion conducting inorganic composite solid electrolyte and method for production thereof | |
| Dash et al. | Study on phase formation and sintering kinetics of BaTi0. 6Zr0. 4O3 powder synthesized through modified chemical route | |
| JP2841344B2 (en) | Piezoelectric ceramic composition | |
| US3248328A (en) | Piezoelectric ceramic composition of lead titanate and 0.1 to 5 mole percent calciumfluoride | |
| DE19847034C2 (en) | Process for the production of a lithium-stabilized Me-ß "Al¶2¶O¶3¶ ceramic and its use | |
| JPH05170413A (en) | Production of hydroxyapatite | |
| JPH1095661A (en) | Production of sodium beta"-alumina compound | |
| JP2001033426A (en) | Solid electrolyte-type carbon dioxide sensor element | |
| JPH013047A (en) | Granular inorganic molded body and its manufacturing method | |
| JPH07106888B2 (en) | Chlorapatite manufacturing method |