JP6339870B2 - Pressure measuring material, manufacturing method thereof, and pressure measuring method - Google Patents
Pressure measuring material, manufacturing method thereof, and pressure measuring method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims description 71
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 110
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 55
- 238000009530 blood pressure measurement Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003086 colorant Substances 0.000 claims description 28
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 7
- 239000003094 microcapsule Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007580 dry-mixing Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Description
本発明は圧力測定用材料とその製造方法並びに圧力測定方法に関するものである。 The present invention relates to a pressure measuring material, a method for manufacturing the same, and a pressure measuring method.
圧力又は圧力分布を色の変化で測定できる圧力測定用材料としては、これまで、電子供与性無色染料前駆体及び電子受容性化合物の発色反応を用いたものが知られている（例えば特許文献１−２）。より詳細には、圧力測定用材料は、電子供与性無色染料前駆体と電子受容性化合物とを有し、電子供与性無色染料前駆体はマイクロカプセルに内包されている。
する。この圧力測定用材料に圧力が加えられると、マイクロカプセルが破壊されて内包物である電子供与性無色染料前駆体が放出され、電子受容性化合物と接触して発色反応する。この色の変化で圧力又は圧力分布を測定するものである。
As pressure measurement materials capable of measuring pressure or pressure distribution by color change, materials using a color reaction of an electron-donating colorless dye precursor and an electron-accepting compound have been known (for example, Patent Document 1). -2). More specifically, the pressure measuring material has an electron donating colorless dye precursor and an electron accepting compound, and the electron donating colorless dye precursor is encapsulated in a microcapsule.
To do. When pressure is applied to the pressure measuring material, the microcapsules are broken and the electron-donating colorless dye precursor, which is an inclusion, is released, and contacts with the electron-accepting compound to cause a color reaction. This change in color measures pressure or pressure distribution.
上記した圧力測定用材料は、マイクロカプセルの破壊を伴う電子供与性無色染料前駆体と電子受容性化合物との発色反応を利用するものである。ここで、マイクロカプセルは界面重合法、相分離法等によって製造され、その製造に適した樹脂によってマイクロカプセル壁が形成される。マイクロカプセルが目的の圧力で破壊されるにはマイクロカプセル壁の壁厚の高度な制御が求められる。このように目的の圧力で破壊されるマイクロカプセルを製造するには適切な樹脂を選択してマイクロカプセル壁の壁厚を高度に制御することが求められるが、その樹脂種が制限されること、マイクロカプセル壁の壁厚の増大には限界があること等から、より高い圧力で破壊されるマイクロカプセルを製造することは難しい。具体的には、３００ＭＰａを越える圧力で破壊されるマイクロカプセルの製造は困難とされている。このため、３００ＭＰａを越える圧力であっても測定することができる圧力測定用材料が望まれているのが実情である。 The above-described pressure measuring material utilizes a color development reaction between an electron-donating colorless dye precursor and an electron-accepting compound accompanied by destruction of microcapsules. Here, the microcapsule is manufactured by an interfacial polymerization method, a phase separation method, or the like, and a microcapsule wall is formed by a resin suitable for the manufacturing. In order for the microcapsule to be broken at a target pressure, a high degree of control of the wall thickness of the microcapsule wall is required. In order to produce a microcapsule that is destroyed at a target pressure in this way, it is required to select an appropriate resin and to highly control the wall thickness of the microcapsule wall, but the type of resin is limited, It is difficult to manufacture a microcapsule that is broken at a higher pressure because there is a limit to the increase in the wall thickness of the microcapsule wall. Specifically, it is difficult to produce microcapsules that are broken at a pressure exceeding 300 MPa. For this reason, the actual situation is that a pressure measurement material that can be measured even at a pressure exceeding 300 MPa is desired.
本発明は、以上のとおりの背景から、３００ＭＰａを越える圧力でも測定可能な圧力測定用材料とその製造方法並びに圧力測定方法を提供することを課題としている。 From the background as described above, an object of the present invention is to provide a pressure measuring material that can be measured even at a pressure exceeding 300 MPa, a manufacturing method thereof, and a pressure measuring method.
上記課題を解決するため、本発明の圧力測定用材料は、非晶質炭酸カルシウムと、水と反応して呈色する呈色剤とを有することを特徴とする。 In order to solve the above-mentioned problems, the pressure measurement material of the present invention is characterized by having amorphous calcium carbonate and a colorant that reacts with water and colors.
この圧力測定用材料においては、前記呈色剤が、無水塩化コバルトであることが好ましい。 In this pressure measurement material, the colorant is preferably anhydrous cobalt chloride.
また、この圧力測定用材料においては、前記非晶質炭酸カルシウムは、含水量１２〜１８質量％の範囲内の非晶質炭酸カルシウムであることが好ましい。 In the pressure measuring material, the amorphous calcium carbonate is preferably amorphous calcium carbonate having a water content of 12 to 18% by mass.
本発明の圧力測定用材料の製造方法は、非晶質炭酸カルシウムと水と反応して呈色する呈色剤含有液とを混合し、次いで前記呈色剤含有液の溶媒を除去して圧力測定用材料を得ることを特徴とする。 In the method for producing a pressure measuring material according to the present invention, amorphous calcium carbonate and a colorant- containing liquid that reacts with water and color is mixed, and then the solvent of the colorant- containing liquid is removed to perform pressure. A material for measurement is obtained.
また、本発明の圧力測定方法は、非晶質炭酸カルシウムと、水と反応して呈色する呈色剤とを用いた圧力測定方法であって、前記非晶質炭酸カルシウムに圧力を加え、当該圧力によって前記非晶質炭酸カルシウムから放出される水で前記呈色剤を呈色させ、その色の変化から前記圧力を求めることを特徴とする。 The pressure measurement method of the present invention is a pressure measurement method using amorphous calcium carbonate and a colorant that reacts with water and colors, and applies pressure to the amorphous calcium carbonate, The colorant is colored with water released from the amorphous calcium carbonate by the pressure, and the pressure is obtained from a change in the color.
本発明によれば、３００ＭＰａを越える圧力でも測定可能な圧力測定用材料とその製造方法並びに圧力測定方法が提供される。 According to the present invention, a pressure measuring material that can be measured even at a pressure exceeding 300 MPa, a manufacturing method thereof, and a pressure measuring method are provided.
以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
本実施形態に係る圧力測定用材料は、非晶質炭酸カルシウムと、水と反応して呈色する呈色剤とを有する。 The pressure measurement material according to this embodiment includes amorphous calcium carbonate and a colorant that reacts with water to develop a color.
非晶質炭酸カルシウムは、化学式ＣａＣＯ３・ｎＨ２Ｏと表される化合物であり、含水炭酸カルシウムである。 Amorphous calcium carbonate is a compound represented by the chemical formula CaCO 3 .nH 2 O, and is hydrous calcium carbonate.
非晶質炭酸カルシウムは、公知の方法によって得ることができる。例えば、T. Yoshino et. al., Cryst. Growth Des., 2012, 12 (7), pp 3357-3361に記載されている方法によって得ることができる。具体的には、０．１Ｍの塩化カルシウム水溶液と０．１Ｍの炭酸ナトリウム水溶液を同量ずつ混合し、吸引ろ過により析出物を分離する。このとき用いられる溶液は氷冷したものが用いられる。吸引ろ過により分離した析出物は氷冷したアセトンで洗浄し、その後真空乾燥等で乾燥することで非晶質炭酸カルシウムを得ることができる。ここで、真空乾燥における真空度を変えることによって、非晶質炭酸カルシウムの含水量を適宜の量に調整することができる。非晶質炭酸カルシウムの含水量が目的とする量になっているかどうかは、熱重量分析によって確認することができる。 Amorphous calcium carbonate can be obtained by a known method. For example, it can be obtained by the method described in T. Yoshino et. Al., Cryst. Growth Des., 2012, 12 (7), pp 3357-3361. Specifically, a 0.1M calcium chloride aqueous solution and a 0.1M sodium carbonate aqueous solution are mixed in equal amounts, and the precipitate is separated by suction filtration. The solution used at this time is ice-cooled. The precipitate separated by suction filtration is washed with ice-cooled acetone, and then dried by vacuum drying or the like to obtain amorphous calcium carbonate. Here, the water content of amorphous calcium carbonate can be adjusted to an appropriate amount by changing the degree of vacuum in vacuum drying. It can be confirmed by thermogravimetric analysis whether or not the water content of the amorphous calcium carbonate is the target amount.
非晶質炭酸カルシウムは、ある一定以上の圧力で加圧すると結晶化する。また、非晶質炭酸カルシウムは、高圧下ではそのほとんどが結晶化し、含水量が大幅に減少する。すなわち、非晶質炭酸カルシウムの結晶化に際して水が放出（脱水）される。放出された水は呈色剤と反応し、呈色剤は呈色する。さらにまた、非晶質炭酸カルシウムが結晶化する圧力は、含水量に依存する。例えば、含水量が多いほど低圧で結晶化する。このため、非晶質炭酸カルシウムの含水量を調整することで結晶化する圧力を変化させることができる。結晶化する圧力を変化させることによって圧力測定の適用範囲も変化させることができる。 Amorphous calcium carbonate crystallizes when pressurized at a certain pressure or higher. Further, most of amorphous calcium carbonate is crystallized under high pressure, and the water content is greatly reduced. That is, water is released (dehydrated) upon crystallization of amorphous calcium carbonate. The released water reacts with the colorant and the colorant is colored. Furthermore, the pressure at which amorphous calcium carbonate crystallizes depends on the water content. For example, the higher the moisture content, the lower the crystallization. For this reason, the crystallization pressure can be changed by adjusting the water content of the amorphous calcium carbonate. By changing the crystallization pressure, the application range of pressure measurement can also be changed.
上記事項は、図１の結果から確認することができる。図１は、非晶質炭酸カルシウムの加圧に伴う脱水量を示したグラフである。より詳細には、含水量１８質量％の非晶質炭酸カルシウムおよび含水量１２質量％の非晶質炭酸カルシウムそれぞれについての加圧に伴う脱水量が示されている。以下に、脱水量測定の手順を示す。 The above items can be confirmed from the results of FIG. FIG. 1 is a graph showing the amount of dehydration accompanying pressurization of amorphous calcium carbonate. More specifically, the amount of dehydration accompanying pressurization for each of amorphous calcium carbonate having a water content of 18% by mass and amorphous calcium carbonate having a water content of 12% by mass is shown. The procedure for measuring the amount of dehydration is shown below.
まず、２種類の真空度（１ｋＰａ、１０Ｐａ）で、それぞれ１日真空乾燥させ、含水量１８質量％、１２質量％の非晶質炭酸カルシウムをそれぞれ得た。次いで、各非晶質炭酸カルシウムを内径１０ｍｍのペレッターに充填し、油圧プレスを用いて、ある一定の圧力で５分間保持した後減圧した。その後非晶質炭酸カルシウムをペレッターから取り出し、熱重量分析により含水量を求めた。 First, each was vacuum-dried for one day at two vacuum degrees (1 kPa, 10 Pa) to obtain amorphous calcium carbonate having a water content of 18% by mass and 12% by mass, respectively. Subsequently, each amorphous calcium carbonate was filled in a pelleter having an inner diameter of 10 mm, and kept at a certain pressure for 5 minutes using a hydraulic press, and then decompressed. Thereafter, amorphous calcium carbonate was taken out from the pelleter, and the water content was determined by thermogravimetric analysis.
図１の結果から、初期含水量１８質量％の非晶質炭酸カルシウムについては加圧圧力の増加につれて単調に脱水量が増加することが明らかとなった。途中、２５０ＭＰａから３７０ＭＰａの間に不連続な変化が見られる。Ｘ線回折の結果からこの圧力範囲で結晶化が起きていることが確認できた。このことから、不連続な脱水量の変化は結晶化のためだと考えられる。また、初期含水量１２質量％の非晶質炭酸カルシウムについては８７０ＭＰａまではほぼ脱水せず、８７０ＭＰａ以上では加圧圧力の増加につれて単調に脱水量が増加することが明らかとなった。この場合も同様にＸ線回折の結果から８７０ＭＰａより高い圧力では非晶質炭酸カルシウムの結晶化が起きていることが確認された。このことから、不連続な脱水量の変化は結晶化のためだと考えられる。 From the results shown in FIG. 1, it has been clarified that the amount of dehydration increases monotonously as the pressurizing pressure increases for amorphous calcium carbonate having an initial water content of 18% by mass. In the middle, a discontinuous change is seen between 250 MPa and 370 MPa. From the result of X-ray diffraction, it was confirmed that crystallization occurred in this pressure range. From this, it is considered that the discontinuous change in the amount of dehydration is due to crystallization. Further, it was revealed that amorphous calcium carbonate having an initial water content of 12% by mass did not substantially dehydrate up to 870 MPa, and that the amount of dehydration increased monotonously as the pressure was increased at 870 MPa or more. Also in this case, from the result of X-ray diffraction, it was confirmed that crystallization of amorphous calcium carbonate occurred at a pressure higher than 870 MPa. From this, it is considered that the discontinuous change in the amount of dehydration is due to crystallization.
本実施形態に用いられる非晶質炭酸カルシウムは、上述のとおり、加圧により結晶化して水が放出される。放出された水は呈色剤と反応し、呈色剤は呈色する。本実施形態に係る圧力測定用材料は、このような非晶質炭酸カルシウムと呈色剤とを有するので、圧力を色の変化で測定することができる。また、非晶質炭酸カルシウムは、３００ＭＰａを越える圧力でも結晶化して加圧に伴う脱水挙動を示す。このため、本実施形態に係る圧力測定用材料は、３００ＭＰａを越える圧力でも測定することができる。また、本実施形態に係る圧力測定用材料は、マイクロカプセルを用いた従来の圧力測定用材料に比べて、圧力測定の適用範囲がより広範化される。 As described above, the amorphous calcium carbonate used in this embodiment is crystallized by pressurization to release water. The released water reacts with the colorant and the colorant is colored. Since the pressure measurement material according to this embodiment has such amorphous calcium carbonate and a colorant, the pressure can be measured by a change in color. Amorphous calcium carbonate crystallizes even at a pressure exceeding 300 MPa and exhibits a dehydration behavior accompanying pressurization. For this reason, the pressure measurement material according to the present embodiment can be measured even at a pressure exceeding 300 MPa. Further, the pressure measurement material according to the present embodiment has a wider range of application for pressure measurement than the conventional pressure measurement material using microcapsules.
本実施形態に係る圧力測定用材料では、含水量が１２〜１８質量％の範囲内の非晶質炭酸カルシウムが好ましく用いられる。含水量がかかる範囲内の非晶質炭酸カルシウムを用いることで、圧力測定用材料では、所定の圧力範囲内でより精度よく色の変化で圧力を測定することができる。例えば、１０〜１０５０ＭＰａの圧力範囲内で色の変化で圧力を測定することができる。 In the pressure measurement material according to the present embodiment, amorphous calcium carbonate having a water content in the range of 12 to 18% by mass is preferably used. By using amorphous calcium carbonate within a range in which the water content is in the range, the pressure measurement material can measure the pressure with a more accurate color change within a predetermined pressure range. For example, the pressure can be measured by a color change within a pressure range of 10 to 1050 MPa.
このような非晶質炭酸カルシウムの含水量は、目的とする圧力測定の適用範囲に応じて適宜設定される。含水量が１２質量％に設定された非晶質炭酸カルシウムを有する圧力測定用材料では５００〜１０５０ＭＰａの圧力範囲内でより精度よく色の変化で圧力を測定することができる。含水量が１８質量％に設定された非晶質炭酸カルシウムを有する圧力測定用材料では１０〜５００ＭＰａの圧力範囲内でより精度よく色の変化で圧力を測定することができる。 The water content of such amorphous calcium carbonate is appropriately set according to the intended application range of pressure measurement. In the pressure measuring material having amorphous calcium carbonate whose water content is set to 12% by mass, the pressure can be measured more accurately with a color change within a pressure range of 500 to 1050 MPa. In the pressure measuring material having amorphous calcium carbonate whose water content is set to 18% by mass, the pressure can be measured with a color change more accurately within a pressure range of 10 to 500 MPa.
本実施形態において用いられる呈色剤は、水と呈色反応するものであれば特に限定されない。発色性や入手の容易性等の観点から、無水塩化コバルト（ＣｏＣｌ２）が好ましいものとして挙げられる。 The colorant used in the present embodiment is not particularly limited as long as it has a color reaction with water. Anhydrous cobalt chloride (CoCl 2 ) is preferable from the viewpoints of color developability and availability.
圧力測定用材料の調製にあたっては、非晶質炭酸カルシウム粉末と、呈色剤（例えば、固体の無水塩化コバルト）とを乾式で混合することができるが、有機溶媒などによる湿式で混合することが好ましい。湿式混合によって得られる圧力測定用材料は、乾式混合によって得られる圧力測定用材料に比べて、色がより均一化し、測定精度がより高まるからである。また、湿式混合は、乾式混合に比べて長時間大気にさらされることがなく、大気中の水蒸気による色の変化をより抑えることができるという利点も有する。 In preparing the pressure measurement material, amorphous calcium carbonate powder and a colorant (for example, solid anhydrous cobalt chloride) can be mixed in a dry manner, but can be mixed in a wet manner with an organic solvent or the like. preferable. This is because the pressure measurement material obtained by wet mixing has a more uniform color and higher measurement accuracy than the pressure measurement material obtained by dry mixing. In addition, wet mixing is not exposed to the atmosphere for a longer time than dry mixing, and has an advantage that color change due to water vapor in the atmosphere can be further suppressed.
湿式混合によって圧力測定用材料を調製するには、非晶質炭酸カルシウムと呈色剤含有液とを混合し、次いで呈色剤含有液の溶媒を除去すればよい。 In order to prepare the pressure measurement material by wet mixing, the amorphous calcium carbonate and the colorant-containing liquid are mixed, and then the solvent of the colorant-containing liquid is removed.
呈色剤含有液は、呈色剤を溶解させる適宜の溶媒を選択し、その溶媒に呈色剤を溶解させることで得ることができる。呈色剤として無水塩化コバルトを用いる場合、溶媒として、例えばアセトンを採用することができる。ここで、無水塩化コバルトの最終濃度が５〜２０質量％となるように、より好ましくは８〜１２質量％となるように呈色剤含有液を調製することが望ましい。無水塩化コバルトの最終濃度が５〜２０質量％の範囲内であれば、やや色が薄い青色〜やや色が濃い青色の圧力測定用材料を得ることができる。無水塩化コバルトの最終濃度が８〜１２質量％の範囲内であれば、最適な色の濃さ（青色）の圧力測定用材料を得ることができる。 The colorant-containing liquid can be obtained by selecting an appropriate solvent that dissolves the colorant and dissolving the colorant in the solvent. When anhydrous cobalt chloride is used as the color former, acetone can be used as the solvent, for example. Here, it is desirable to prepare the colorant-containing liquid so that the final concentration of anhydrous cobalt chloride is 5 to 20% by mass, and more preferably 8 to 12% by mass. If the final concentration of anhydrous cobalt chloride is in the range of 5 to 20% by mass, a pressure measurement material having a slightly lighter color to a slightly darker color can be obtained. When the final concentration of anhydrous cobalt chloride is in the range of 8 to 12% by mass, a pressure measuring material having an optimum color density (blue) can be obtained.
非晶質炭酸カルシウムと呈色剤含有液とを混合した後の呈色剤含有液の溶媒の除去は、例えば、減圧下で蒸発乾固させることによって行われる。こうして粉末状の圧力測定用材料を得ることができる。 The removal of the solvent of the colorant-containing liquid after mixing the amorphous calcium carbonate and the colorant-containing liquid is performed, for example, by evaporating to dryness under reduced pressure. Thus, a powdery pressure measuring material can be obtained.
調製方法による圧力測定用材料の色の違い（呈色剤の混ざり具合）を調べた結果を図２に示す。図２（ａ）は乾式混合によって製造された圧力測定用材料の加圧物の外観写真であり、図２（ｂ）は湿式混合によって製造された圧力測定用材料の加圧物の外観写真である。圧力測定用材料は上記のとおり粉末状のものとして得られるため、このままでは色の違いを示すのが難しい。このため、当該圧力測定用材料をハンドプレスで加圧（仮押し）し、その被プレス部分の外観を観察した。なお、ハンドプレスによる加圧は、圧力測定用材料の色の違いを観察できる程度に行われ、圧力測定用材料に対する圧力の影響がなるべく少なくなるようにした。図２（ａ）（ｂ）それぞれの圧力測定用材料の加圧物は次のようにして得た。 FIG. 2 shows the result of examining the color difference (mixing condition of the colorant) of the pressure measurement material by the preparation method. FIG. 2A is an appearance photograph of a pressure measurement material manufactured by dry mixing, and FIG. 2B is an appearance photograph of a pressure measurement material manufactured by wet mixing. is there. Since the pressure measuring material is obtained as a powder as described above, it is difficult to show the color difference as it is. Therefore, the pressure measurement material was pressed (temporarily pressed) with a hand press, and the appearance of the pressed part was observed. In addition, pressurization by a hand press was performed to such an extent that the difference in color of the pressure measurement material could be observed, so that the influence of the pressure on the pressure measurement material was minimized. Pressurized materials for the respective pressure measuring materials shown in FIGS. 2A and 2B were obtained as follows.
図２（ａ）の圧力測定用材料の加圧物は、固体の無水塩化コバルトをメノウ乳鉢で粉砕したものと粉末非晶質炭酸カルシウムとの混合物（圧力測定用材料）をハンドプレスで仮押しして得た。図２（ｂ）の圧力測定用材料の加圧物は、含水量１８質量％の非晶質炭酸カルシウムと無水塩化コバルトのアセトン溶液とを混合し、蒸発乾固させ、得られた粉状物（圧力測定用材料）をハンドプレスで仮押しして得た。なお、無水塩化コバルトの最終濃度が１０質量％となるようにアセトン溶液が調製された。 Pressurized material for pressure measurement in FIG. 2 (a) is a temporary press of a mixture of solid anhydrous cobalt chloride pulverized in an agate mortar and powdered amorphous calcium carbonate (pressure measurement material) with a hand press. I got it. The pressurized material of the pressure measurement material in FIG. 2 (b) was prepared by mixing amorphous calcium carbonate having a water content of 18% by mass with an acetone solution of anhydrous cobalt chloride, and evaporating to dryness. (Pressure measurement material) was obtained by temporary pressing with a hand press. An acetone solution was prepared so that the final concentration of anhydrous cobalt chloride was 10% by mass.
図２の結果から、（ｂ）の湿式混合による圧力測定用材料の加圧物は（ａ）の乾式混合による圧力測定用材料の加圧物よりも色がより均一化していることが確認された。 The result of FIG. 2 confirms that the pressure of the pressure measurement material by wet mixing in (b) is more uniform in color than the pressure measurement material by dry mixing in (a). It was.
本実施形態に係る圧力測定用材料は粉末状のものとして用いることができる。このような粉末状の圧力測定用材料を用いて圧力を測定するには、当該圧力測定用材料を被測定箇所にそのまま散布すればよい。また、粉末状の圧力測定用材料を樹脂やパルプ等に混合してシート状に加工して用いることもできる。 The pressure measurement material according to this embodiment can be used as a powder. In order to measure the pressure using such a powdery pressure measurement material, the pressure measurement material may be sprayed as it is to the measurement site. Further, a powdery pressure measurement material can be mixed with resin, pulp, or the like and processed into a sheet shape for use.
以下に実施例を示し、さらに詳しく説明する。もちろん以下の例によって本発明が限定されることはない。 Hereinafter, examples will be shown and described in more detail. Of course, the present invention is not limited to the following examples.
＜実施例１＞
含水量１８質量％の非晶質炭酸カルシウムと無水塩化コバルトのアセトン溶液を混ぜ、蒸発乾固させることで作製した圧力測定用材料を得た。無水塩化コバルトの最終濃度が１０質量％となるように調整した。得られた圧力測定用材料を内径１０ｍｍのペレッターに充填し、油圧プレスによって、ある一定の圧力で３０秒間保持した後減圧した。その後圧力測定用材料をペレッターから取り出し、色の変化を肉眼及び分光光度計を用いた反射スペクトル測定（反射率測定）により評価した。肉眼の観察からは圧力の増加につれて青色から赤紫色へと変化することが確認できた（図３（ａ））。反射率の測定は入射角度４５度に対して反射角度９０度方向に積分球を設置し行った。その結果を図４（ａ）に示す。得られた反射スペクトルの８２０ｎｍ以上８４０ｎｍ以下の反射率について平均値をとり、その値で得られた反射スペクトルを規格化した。その結果を図４（ｂ）に示す。その後、以下の式に従って、波長４００ｎｍでの反射率の変化量ΔＲｎを求めた。ΔＲｎを色の指標とした。
<Example 1>
An amorphous calcium carbonate having a water content of 18% by mass and an acetone solution of anhydrous cobalt chloride were mixed and evaporated to dryness to obtain a pressure measurement material. The final concentration of anhydrous cobalt chloride was adjusted to 10% by mass. The obtained material for pressure measurement was filled in a pelleter having an inner diameter of 10 mm, and kept at a certain pressure for 30 seconds by a hydraulic press, and then the pressure was reduced. Thereafter, the pressure measurement material was taken out from the pelleter, and the color change was evaluated by reflection spectrum measurement (reflectance measurement) using the naked eye and a spectrophotometer. From the naked eye, it was confirmed that the pressure changed from blue to reddish purple as the pressure increased (FIG. 3 (a)). The reflectance was measured by installing an integrating sphere in the direction of 90 ° reflection angle with respect to the incident angle of 45 °. The result is shown in FIG. The average value was taken about the reflectance of 820 nm or more and 840 nm or less of the obtained reflection spectrum, and the obtained reflection spectrum was normalized. The result is shown in FIG. Thereafter, the amount of change ΔR n in reflectance at a wavelength of 400 nm was determined according to the following formula. The ΔR n was the color index of.
ΔＲｎ ＝ Ｒｒ −Ｒｎ ΔR n = R r −R n
Ｒｎ：圧力ｎＭＰａで加圧した圧力測定用材料の波長４００ｎｍでの反射率。ただし、８２０ｎｍ以上８４０ｎｍ以下の反射率の平均値で規格化したもの。
Ｒｒ：制御可能な範囲で最も低圧力な条件（実施例１では１０ＭＰａ、実施例２では１２０ＭＰａ）で加圧した圧力測定用材料の波長４００ｎｍでの反射率。ただし、８２０ｎｍ以上８４０ｎｍ以下の反射率の平均値で規格化したもの。
R n : reflectivity at a wavelength of 400 nm of a material for pressure measurement pressurized at a pressure of nMPa. However, those normalized by the average reflectance of 820 nm or more and 840 nm or less.
R r : reflectivity at a wavelength of 400 nm of the pressure measurement material pressed under the lowest pressure condition within the controllable range (10 MPa in Example 1, 120 MPa in Example 2). However, those normalized by the average reflectance of 820 nm or more and 840 nm or less.
反射スペクトルの解析から求まった色の指標ΔＲｎを図５に示す。１０ＭＰａ以上５００ ＭＰａ以下の圧力範囲において色の指標は圧力の増加につれて単調に増加することがわかった。含水量１８質量％の非晶質炭酸カルシウムから作製した圧力測定用材料の圧力に対する色の変化の仕方は含水量１８質量％の非晶質炭酸カルシウムの圧力に対する脱水量の変化（図１）と同様の傾向を見せた。 The color index ΔR n obtained from the analysis of the reflection spectrum is shown in FIG. It was found that the color index increased monotonously as the pressure increased in the pressure range of 10 MPa to 500 MPa. The pressure change of the pressure measuring material made from amorphous calcium carbonate with a water content of 18% by mass is based on the change in dehydration amount with respect to the pressure of the amorphous calcium carbonate with a water content of 18% by mass (FIG. 1). A similar trend was shown.
＜実施例２＞
含水量１２質量％の非晶質炭酸カルシウムと無水塩化コバルトのアセトン溶液を混ぜ、蒸発乾固させることで作製した圧力測定用材料を得た。無水塩化コバルトの最終濃度が１０質量％となるように調整した。得られた圧力測定用材料を内径１０ｍｍのペレッターに充填し、油圧プレスによって、ある一定の圧力で３０秒間保持した後減圧した。その後圧力測定用材料をペレッターから取り出し、色の変化を肉眼及び分光光度計を用いた反射スペクトル測定により評価した。肉眼の観察からは圧力の増加につれて青色から青紫色へと変化することが確認できた（図３（ｂ））。また、前述の方法で反射スペクトルを解析し、波長４００ｎｍでの反射率の変化量を求めたところ、５００ＭＰａまでは一定で変化がないのに対して、５００ＭＰａ以上１０５０ＭＰａ以下の圧力範囲では加圧圧力の増加につれて色の指標が単調に増加した（図５）。含水量１２質量％の非晶質炭酸カルシウムから作製した圧力測定用材料の圧力に対する色の変化の仕方は含水量１２質量％の非晶質炭酸カルシウムの圧力に対する脱水量の変化（図１）と同様の傾向を見せた。
<Example 2>
An amorphous calcium carbonate having a water content of 12% by mass and an acetone solution of anhydrous cobalt chloride were mixed and evaporated to dryness to obtain a pressure measurement material. The final concentration of anhydrous cobalt chloride was adjusted to 10% by mass. The obtained material for pressure measurement was filled in a pelleter having an inner diameter of 10 mm, and kept at a certain pressure for 30 seconds by a hydraulic press, and then the pressure was reduced. Thereafter, the pressure measurement material was taken out of the pelleter, and the color change was evaluated by reflection spectrum measurement using the naked eye and a spectrophotometer. From the naked eye, it was confirmed that the pressure changed from blue to blue-violet as the pressure increased (FIG. 3B). Further, the reflection spectrum was analyzed by the above-described method, and the amount of change in the reflectance at a wavelength of 400 nm was determined. While it was constant up to 500 MPa and not changed, the pressure range was from 500 MPa to 1050 MPa. The color index increased monotonously as the value increased (FIG. 5). The pressure change of the pressure measuring material made from amorphous calcium carbonate with a water content of 12% by mass is based on the change in dehydration amount with respect to the pressure of the amorphous calcium carbonate with a water content of 12% by mass (FIG. 1). A similar trend was shown.
Claims (5)
前記非晶質炭酸カルシウムに圧力を加え、当該圧力によって前記非晶質炭酸カルシウムから放出される水で前記呈色剤を呈色させ、その色の変化から前記圧力を求めることを特徴とする圧力測定方法。 A pressure measurement method using amorphous calcium carbonate and a colorant that reacts with water and colors,
Pressure is applied to the amorphous calcium carbonate, the colorant is colored with water released from the amorphous calcium carbonate by the pressure, and the pressure is obtained from a change in the color. Measuring method.
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