JP6284194B2 - Stress quenching material, stress quencher, and method of manufacturing stress quenching material - Google Patents
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Description
本発明は、機械的な外力が加えられることにより消光する応力消光材料及び応力消光体、並びに応力消光材料の製造方法に関する。 The present invention relates to a stress-quenching material and a stress-quenching material that are quenched by applying a mechanical external force, and a method for producing a stress-quenching material.
従来、物質が外部から刺激を与えられることによって、室温付近で発光する現象は、いわゆる蛍光現象としてよく知られている。 Conventionally, a phenomenon in which a substance emits light near room temperature when externally stimulated is well known as a so-called fluorescent phenomenon.
このような蛍光現象を生じる物質、すなわち蛍光体は、蛍光ランプなどの照明灯や、CRT(Cathode Ray Tube)いわゆるブラウン管などのディスプレイなどとして用いられている。 A substance that generates such a fluorescent phenomenon, that is, a phosphor, is used as an illumination lamp such as a fluorescent lamp or a display such as a cathode ray tube (CRT) so-called cathode ray tube.
この蛍光現象を生じさせる外部からの刺激は、通常、紫外線、電子線、Ｘ線、放射線、電界、化学反応などによって与えられているが、機械的な外力などの刺激を加えて変形させることによって強く発光する材料については、長らく知られていなかった。 External stimuli that cause this fluorescent phenomenon are usually given by ultraviolet rays, electron beams, X-rays, radiation, electric fields, chemical reactions, etc., but they can be deformed by applying stimuli such as mechanical external forces. A material that emits intense light has not been known for a long time.
そこで、本発明者が所属する研究機関において鋭意研究が行われた結果、機械的な外力により生じる変形によって発光する、これまでに知られていない新規な発光材料が提案された（例えば、特許文献１〜６参照。）。 Therefore, as a result of intensive studies at the research institution to which the present inventor belongs, a novel light-emitting material that has not been known so far that emits light due to deformation caused by a mechanical external force has been proposed (for example, patent literature) 1-6.)
このような発光材料は、その後応力発光材料と称され、現在では、新規な計測技術として、既設土木構造物の維持管理における非破壊検査技術や構造物の部材の応力分布の可視化技術などの応用研究が盛んに行われている（例えば、特許文献７参照。）。 Such luminescent materials are later referred to as stress luminescent materials, and are now applied as new measurement technologies such as non-destructive inspection technology for maintaining existing civil engineering structures and visualization technology for stress distribution of structural members. Research has been actively conducted (for example, see Patent Document 7).
上述の通り、従来の応力発光材料は応力を受けることで発光を示すものであるが、蛍光を発している状態で応力を受けると消光する材料（以下、応力消光材料ともいう。）については、今日に至るまで未だ知られていない。 As described above, a conventional stress-stimulated luminescent material emits light when subjected to stress. However, a material that quenches when stressed in a fluorescent state (hereinafter also referred to as a stress-quenched material) is described below. Not yet known until today.
本発明は、斯かる事情に鑑みてなされたものであって、応力を受けることにより蛍光が減衰または消光する応力消光材料を提供する。また本発明では、応力消光材料を含有する応力消光体や、応力消光材料の製造方法についても提供する。 The present invention has been made in view of such circumstances, and provides a stress-quenching material in which fluorescence is attenuated or quenched by receiving stress. The present invention also provides a stress quencher containing a stress quencher material and a method for producing the stress quencher material.
上記従来の課題を解決するために、本発明では、Cuイオンが固溶したCaZnOSの結晶体を含有する応力消光材料を提供する。 In order to solve the above conventional problems, the present invention provides a stress quenching material containing a CaZnOS crystal in which Cu ions are dissolved.
また、本発明の更なる具体的態様として、前記Cuイオンは、母体材料としてのCaZnOS中に含まれるZnの0.005〜8mol%に相当する濃度で固溶していることとしても良い。 As a further specific embodiment of the present invention, the Cu ions may be dissolved in a concentration corresponding to 0.005 to 8 mol% of Zn contained in CaZnOS as a base material.
また、本発明の更なる具体的態様として、前記Cuイオンは、前記Znの少なくとも一部を置換していることとしても良い。 As a further specific aspect of the present invention, the Cu ions may substitute at least a part of the Zn.
また、本発明では、第１のトラップ準位に捕捉された励起状態のキャリアが前記第１のトラップ準位よりも低い安定準位へ遷移する際の差分のエネルギーにより発光を示す材料において、応力の付与により前記第１のトラップ準位のキャリアが遷移する第２のトラップ準位有し、付与された応力に応じて前記第１のトラップ準位から前記安定準位へ遷移可能なキャリア数を減ずることにより消光を示すべく構成したことを特徴とする応力消光材料についても提供する。 Further, in the present invention, in a material that emits light by energy of a difference when excited carriers trapped in the first trap level transition to a stable level lower than the first trap level, The number of carriers that have a second trap level in which carriers of the first trap level transition by the application of the first trap level and can transition from the first trap level to the stable level in accordance with the applied stress. The present invention also provides a stress-quenching material that is configured to exhibit extinction by being reduced.
また、本発明では、更に別の形態として、上述の応力消光材料を所定のマトリクス材料中に分散させて形成した応力消光体を提供する。 Moreover, in this invention, the stress quencher formed by disperse | distributing the above-mentioned stress quenching material in a predetermined matrix material as another form is provided.
また、本発明では、更に別の形態として、上述の応力消光材料の消光による応力検出のための使用を提供する。 Moreover, in this invention, use for the stress detection by quenching of the above-mentioned stress quenching material is provided as another form.
また、本発明では、更に別の形態として、1〜3モル部のカルシウムを含有するカルシウム化合物の粉末と、1±0.1モル部の亜鉛を含有する亜鉛化合物の粉末と、1±0.1モル部の硫黄を含有する硫黄化合物の粉末と、前記亜鉛化合物に含まれる亜鉛量の0.005〜8mol%に相当する銅を含有する銅化合物の粉末とを混合して混合物を得る工程と、前記混合物を焼成することによりCuイオンが固溶したCaZnOSの結晶体を含む焼成物を生成する工程と、前記焼成物を冷却して応力消光材料を生成する冷却工程と、を有することを特徴とする応力消光材料の製造方法を提供する。 Further, in the present invention, as still another embodiment, a calcium compound powder containing 1 to 3 mol parts of calcium, a zinc compound powder containing 1 ± 0.1 mol parts of zinc, and 1 ± 0.1 mol parts of calcium powder A step of mixing a sulfur compound powder containing sulfur and a copper compound powder containing copper corresponding to 0.005 to 8 mol% of zinc contained in the zinc compound to obtain a mixture, and firing the mixture A process for producing a fired product containing CaZnOS crystals in which Cu ions are dissolved, and a cooling process for producing a stress quenching material by cooling the fired product. A manufacturing method is provided.
本発明に係る応力消光材料では、Cuイオンが固溶したCaZnOSの結晶体を含有することとしたため、応力を受けることにより蛍光が減衰または消光する応力消光材料を提供することができる。 Since the stress-quenching material according to the present invention contains a CaZnOS crystal in which Cu ions are dissolved, it is possible to provide a stress-quenching material in which fluorescence is attenuated or quenched by receiving stress.
また、前記Cuイオンは、母体材料としてのCaZnOS中に含まれるZnの0.005〜8mol%に相当する濃度で固溶させることで、消光をより堅実に行わせることができる。 Moreover, quenching can be performed more firmly by dissolving the Cu ions at a concentration corresponding to 0.005 to 8 mol% of Zn contained in CaZnOS as a base material.
また、前記Cuイオンは、前記Znの少なくとも一部を置換していることとすれば、消光をより堅実に行わせることができる。 Moreover, if the said Cu ion is substituting at least one part of said Zn, it can make quenching more steady.
また、本発明に係る応力消光材料では、第１のトラップ準位に捕捉された励起状態のキャリアが前記第１のトラップ準位よりも低い安定準位へ遷移する際の差分のエネルギーにより発光を示す材料において、応力の付与により前記第１のトラップ準位のキャリアが遷移する第２のトラップ準位有し、付与された応力に応じて前記第１のトラップ準位から前記安定準位へ遷移可能なキャリア数を減ずることにより消光を示すべく構成したため、応力を受けることにより蛍光が減衰または消光する応力消光材料を提供することができる。 In the stress-quenching material according to the present invention, the excited state carriers trapped in the first trap level emit light by the energy of the difference when transitioning to a stable level lower than the first trap level. The material shown has a second trap level in which carriers in the first trap level transition due to application of stress, and transitions from the first trap level to the stable level in accordance with the applied stress. Since it is configured to exhibit quenching by reducing the number of possible carriers, it is possible to provide a stress quenching material in which fluorescence is attenuated or quenched by receiving stress.
また、本発明に係る応力消光体では、上述の応力消光材料を所定のマトリクス材料中に分散させて形成することで、応力を受けることにより蛍光が減衰または消光する応力消光体を提供することができる。 Further, in the stress quencher according to the present invention, it is possible to provide a stress quencher in which fluorescence is attenuated or quenched by receiving stress by forming the above-described stress quencher material dispersed in a predetermined matrix material. it can.
また、本発明では、上述の応力消光材料を消光による応力検出のために使用することとしたため、消光によって応力を検出することができる。 In the present invention, since the above-mentioned stress quenching material is used for stress detection by quenching, the stress can be detected by quenching.
また、本発明に係る応力消光材料の製造方法では、1〜3モル部のカルシウムを含有するカルシウム化合物の粉末と、1±0.1モル部の亜鉛を含有する亜鉛化合物の粉末と、1±0.1モル部の硫黄を含有する硫黄化合物の粉末と、前記亜鉛化合物に含まれる亜鉛量の0.005〜8mol%に相当する銅を含有する銅化合物の粉末とを混合して混合物を得る工程と、前記混合物を焼成することによりCuイオンが固溶したCaZnOSの結晶体を含む焼成物を生成する工程と、前記焼成物を冷却して応力消光材料を生成する冷却工程と、を有することとしたため、応力を受けることにより蛍光が減衰または消光する応力消光材料の製造方法を提供することができる。 In the method for producing a stress quenching material according to the present invention, a calcium compound powder containing 1 to 3 mol parts of calcium, a zinc compound powder containing 1 ± 0.1 mol parts of zinc, and 1 ± 0.1 mol A step of mixing a sulfur compound powder containing a part of sulfur and a copper compound powder containing copper corresponding to 0.005 to 8 mol% of zinc contained in the zinc compound to obtain a mixture; and It is stressed because it has a step of producing a fired product containing a CaZnOS crystal in which Cu ions are dissolved by firing and a step of cooling the fired product to produce a stress-quenching material. Thus, it is possible to provide a method for producing a stress-quenching material in which fluorescence is attenuated or quenched.
本発明は、Cuイオンが固溶したCaZnOSの結晶体を含有する応力消光材料を提供するものである。ここで応力消光材料とは、応力の増加に対して発光強度が減少するというMechanical quenching(MQ)現象を示すものである。 The present invention provides a stress-quenching material containing a CaZnOS crystal in which Cu ions are dissolved. Here, the stress quenching material indicates a mechanical quenching (MQ) phenomenon in which the emission intensity decreases with increasing stress.
Cuイオンは、後に試験データを参照しつつ説明するが、母体材料としてのCaZnOS中に含まれるZnの0.005〜8mol%に相当する濃度で固溶させるのが望ましい。0.005mol%を下回るとMQ現象が生起されなくなるため好ましくない。また、8mol%を上回っても顕著なMQ現象が生起されなくなるため好ましくない。CuイオンをCaZnOS中に含まれるZnの0.005mol%以上、8mol%以下に相当する濃度範囲で固溶させることにより、MQ現象を堅実に生起させることができる。また、濃度範囲を0.005mol%以上、6mol%以下、好ましくは0.005mol%以上、4mol%以下、より好ましくは0.005mol%以上、2mol%以下、更に好ましくは0.005mol%以上、0.4mol%以下、更に好ましくは0.005mol%以上、0.2mol%以下、更に好ましくは0.005mol%以上、0.1mol%以下、更に好ましくは0.005mol%以上、0.05mol%以下とすることで、より効果的にMQ現象を生起できる応力消光材料を提供することができる。なお、Cuイオンは、１価(Cu+)又は２価(Cu2+)のいずれであっても良い。 Although Cu ions will be described later with reference to test data, it is desirable to dissolve them at a concentration corresponding to 0.005 to 8 mol% of Zn contained in CaZnOS as a base material. If it is less than 0.005 mol%, the MQ phenomenon will not occur, such being undesirable. Further, even if it exceeds 8 mol%, a remarkable MQ phenomenon is not caused, which is not preferable. By dissolving Cu ions in a concentration range corresponding to 0.005 mol% or more and 8 mol% or less of Zn contained in CaZnOS, the MQ phenomenon can be steadily caused. Further, the concentration range is 0.005 mol% or more, 6 mol% or less, preferably 0.005 mol% or more, 4 mol% or less, more preferably 0.005 mol% or more, 2 mol% or less, more preferably 0.005 mol% or more, 0.4 mol% or less, More preferably 0.005 mol% or more, 0.2 mol% or less, more preferably 0.005 mol% or more, 0.1 mol% or less, more preferably 0.005 mol% or more, 0.05 mol% or less, more effectively MQ phenomenon. A stress quenching material that can occur can be provided. The Cu ion may be monovalent (Cu + ) or divalent (Cu 2+ ).
また、このような濃度で添加したCuイオンは、母体材料を構成するCaZnOS中のZnの少なくとも一部を置換する状態で固溶していても良い。より具体的には、本実施形態に係る応力消光材料の一形態として非化学量論的組成（化学量論的化学組成式から逸脱する化学組成式を有する組成）で表すならば、CaZn1-xCuxOS(0.00005≦x≦0.08)とすることができる。 Further, the Cu ions added at such a concentration may be dissolved in a state in which at least a part of Zn in CaZnOS constituting the base material is replaced. More specifically, if expressed as a non-stoichiometric composition (a composition having a chemical composition formula deviating from the stoichiometric chemical composition formula) as one form of the stress quenching material according to the present embodiment, CaZn 1− x Cu x OS (0.00005 ≦ x ≦ 0.08).
本発明の理解に供すべく、本実施形態に係る応力消光材料の一例として敢えて限定的に表現するならば、CaZnOS結晶中に含まれるZnの0.005mol%以上8mol%以下をCuイオンで置換することにより、この置換された結晶体の蛍光放射時に応力を付与することで前記蛍光の放射を減衰又は消光させるべく構成した応力消光材料であるとも言える。また、母体材料であるCaZnOS結晶を構成するZnのうち0.005mol%以上8mol%以下がCuイオンに置換された結晶体を含むものであるとも言える。 For the purpose of understanding the present invention, if expressed in a limited manner as an example of the stress quenching material according to the present embodiment, 0.005 mol% or more and 8 mol% or less of Zn contained in the CaZnOS crystal is replaced with Cu ions. Thus, it can be said that the stress-quenching material is configured to attenuate or quench the fluorescence emission by applying stress at the time of fluorescence emission of the substituted crystal. In addition, it can be said that 0.005 mol% or more and 8 mol% or less of Zn constituting the CaZnOS crystal which is the base material includes a crystal body substituted with Cu ions.
ところで、本実施形態に係る応力消光材料の消光に係るメカニズムについてであるが、本発明者らは以下のようなメカニズムで現象が生起しているものと考えている。 By the way, regarding the mechanism related to the quenching of the stress-quenching material according to the present embodiment, the present inventors consider that the phenomenon occurs by the following mechanism.
図１中において(1)で示すように、まず、安定準位にある銅のキャリアが励起光の照射により伝導帯(CB)に励起される（励起過程）。 As shown by (1) in FIG. 1, first, the copper carrier at the stable level is excited to the conduction band (CB) by irradiation with excitation light (excitation process).
次に、(2)で示すように、励起されたキャリアは母体材料中に存在する欠陥準位（第１のトラップ準位）にトラップされる（トラップ過程）。 Next, as shown in (2), the excited carriers are trapped in a defect level (first trap level) existing in the base material (trap process).
ここで、応力が付与されていない場合には、(3)で示すように、環境中の熱エネルギーにより第１のトラップ準位より離脱し（離脱過程）、一旦酸素や硫黄の欠陥準位にトラップされて元の安定準位に戻ることとなる（再結合過程）。 Here, when no stress is applied, as shown in (3), it is detached from the first trap level by the thermal energy in the environment (detachment process), and once reaches the defect level of oxygen or sulfur. It is trapped and returns to the original stable level (recombination process).
ところが、応力消光材料に応力が付与されると、前述のトラップ過程(2)を経て母体材料中の第１のトラップ準位にトラップされたキャリアが、(5)で示すように亜鉛の欠陥により生じたトラップ準位（第２のトラップ準位）に遷移することとなり（消光過程）、前述の離脱過程(3)や再結合過程(4)へ供給されるキャリア量が減少し、減光や消光現象が生起することとなる。 However, when stress is applied to the stress quenching material, the carriers trapped in the first trap level in the base material through the trapping process (2) described above are caused by zinc defects as shown in (5). Transition to the generated trap level (second trap level) (quenching process), the amount of carriers supplied to the above-mentioned separation process (3) and recombination process (4) decreases, A quenching phenomenon will occur.
このように、本実施形態に係る応力消光材料は、第１のトラップ準位に捕捉された励起状態のキャリアが前記第１のトラップ準位よりも低い安定準位へ遷移する際の差分のエネルギーにより発光を示す材料において、応力の付与により前記第１のトラップ準位のキャリアが遷移する第２のトラップ準位有し、付与された応力に応じて前記第１のトラップ準位から前記安定準位へ遷移可能なキャリア数を減ずることにより消光を示すべく構成したものであるとも言える。 As described above, the stress-quenching material according to the present embodiment has the difference energy when carriers in the excited state trapped in the first trap level transition to a stable level lower than the first trap level. In the material that emits light, the second trap level in which carriers of the first trap level transition due to the application of stress has, and the stable level is changed from the first trap level in accordance with the applied stress. It can also be said that it is configured to show quenching by reducing the number of carriers that can be shifted to the position.
すなわち、本明細書では母体材料をCaZnOSとしてCuをドープすることにより上述のメカニズムを実現してMQ現象を生起する応力消光材料を中心に説明するが、母体材料やドープする物質は必ずしもこれらに限定されるものではなく、上述のメカニズムを実現可能な物質であれば本発明の概念に含まれると解するべきである。但し、本発明において母体材料やドープする物質を特定の物質に限定することも妨げない。 That is, in this specification, the description will focus on stress quenching materials that realize the above-described mechanism by doping Cu with CaZnOS as the base material and cause the MQ phenomenon, but the base material and the substance to be doped are not necessarily limited to these. It should be understood that any substance that can realize the above-described mechanism is included in the concept of the present invention. However, in the present invention, it is not prohibited to limit the base material or the substance to be doped to a specific substance.
また、上述した本実施形態に係る応力消光材料は、所定のマトリクス材料中に分散させて応力消光体を形成させても良い。例えば、硬化性を有する樹脂をマトリクス材料とし、硬化前の樹脂中に粉末状の応力消光材料を分散させ硬化させることにより、応力を付与することで消光や減光を示す所望の形状の応力消光体を容易に形成することができる。なお、マトリクス材料は少なくとも、同マトリクス材料中に混在させた応力消光材料を励起させるための励起光や、応力消光材料から放射される蛍光が透過可能なものが用いられる。 The stress quencher material according to the present embodiment described above may be dispersed in a predetermined matrix material to form a stress quencher. For example, a resin having a curing property is used as a matrix material, and a powder-like stress quenching material is dispersed and cured in the resin before curing, thereby applying a stress to quenching or dimming the desired shape. The body can be easily formed. Note that at least the matrix material that can transmit excitation light for exciting the stress quenching material mixed in the matrix material and fluorescence emitted from the stress quenching material is used.
また、本発明は、前述のような応力消光材料の製造方法を提供するものでもある。 The present invention also provides a method for producing the stress quenching material as described above.
具体的には、本実施形態に係る応力消光材料の製造方法では、1〜3モル部のカルシウムを含有する量のカルシウム化合物の粉末と、1±0.1モル部の亜鉛を含有する量の亜鉛化合物の粉末と、1±0.1モル部の硫黄を含有する量の硫黄化合物の粉末と、前記亜鉛化合物の粉末中に含まれる亜鉛量の0.005〜8mol%に相当する銅を含有する量の銅化合物の粉末とを混合して混合物を得る工程と、前記混合物を焼成することによりCuイオンが固溶したCaZnOSの結晶体を含む焼成物を生成する工程と、前記焼成物を冷却して応力消光材料を生成する冷却工程と、を有することを特徴としている。 Specifically, in the method for producing a stress-quenching material according to the present embodiment, a powder of calcium compound in an amount containing 1 to 3 mole parts of calcium and a zinc compound in an amount containing 1 ± 0.1 mole parts of zinc. A powder of sulfur compound in an amount containing 1 ± 0.1 mol part of sulfur, and an amount of copper compound in an amount of copper corresponding to 0.005 to 8 mol% of zinc contained in the zinc compound powder. A step of mixing the powder to obtain a mixture, a step of producing a fired product containing CaZnOS crystals in which Cu ions are dissolved by firing the mixture, and cooling the fired product to obtain a stress quenching material. And a cooling step to be generated.
混合工程にて使用するカルシウム化合物や、亜鉛化合物、硫黄化合物、銅化合物は、応力消光材料の組成比率に影響を及ぼすものでなければ特に限定されるものではなく、例えば、炭酸塩、硝酸塩、塩化物、硫化物、酸化物、シュウ酸塩、酢酸塩、水酸化物などを用いることができる。また、硫化亜鉛(ZnS)のように、亜鉛化合物でもあり硫黄化合物でもある化合物を使用することもできる。 The calcium compound, zinc compound, sulfur compound, and copper compound used in the mixing step are not particularly limited as long as they do not affect the composition ratio of the stress quenching material. For example, carbonate, nitrate, chloride An oxide, sulfide, oxide, oxalate, acetate, hydroxide or the like can be used. A compound that is both a zinc compound and a sulfur compound, such as zinc sulfide (ZnS), can also be used.
本実施形態に係る応力消光材料の製造方法においてカルシウム化合物は、好ましくは1〜3モル部使用する。母体材料としてのCaZnOSを調製するためには、化学量論比（Ca:Zn:S=1:1:1）に従い、各化合物中のCaやZn、Sがそれぞれ略１モル部ずつとなる大凡等しい割合で調合すべきと考えられるが、本発明者らの研究過程における経験上、このよううな比率で調合して焼成過程に供しても、Zn系の副生成物が多く生成してしまい、CaZnOSの単相も得られるものの効率的ではないことが分かっている。 In the method for producing a stress quenching material according to this embodiment, the calcium compound is preferably used in an amount of 1 to 3 mole parts. In order to prepare CaZnOS as a base material, according to the stoichiometric ratio (Ca: Zn: S = 1: 1: 1), Ca, Zn, and S in each compound are each approximately 1 mol part. Although it is thought that it should be blended at an equal ratio, even if it is blended at such a ratio and subjected to the firing process based on the experience in the research process of the present inventors, a lot of Zn-based by-products are generated, Although a single phase of CaZnOS is obtained, it has been found to be inefficient.
そこで、本実施形態に係る応力消光材料の製造方法では、ZnやSがそれぞれ略１モル部ずつとなるように亜鉛化合物や硫黄化合物を用いた場合、カルシウム化合物の量は、同カルシウム化合物中に含まれるカルシウムが１モル部を越えるように過剰量を添加しても良いこととしている。過剰量となるカルシウムの量は、１モル部を超える量であって、CaZnOSの単相が得られる量であれば特に限定されるものではない。 Therefore, in the method for producing a stress quenching material according to the present embodiment, when a zinc compound or a sulfur compound is used so that each of Zn and S is approximately 1 mol part, the amount of the calcium compound is in the calcium compound. An excess amount may be added so that the contained calcium exceeds 1 mol part. An excessive amount of calcium is not particularly limited as long as it is an amount exceeding 1 mole part and can provide a single phase of CaZnOS.
しかしながら、本発明者らの研究によれば、カルシウムの量が１モル部を超える量であっても、１モル部に近い量であれば前述のZn系の副生成物としてのZnS等やその他の副生成物としてCaOの生成が認められ、1.5モル部に近づくほどZnSの生成は抑制される。また、1.5モル部を越えると徐々に副製するCaOの増加が認められることとなる。 However, according to the study by the present inventors, even if the amount of calcium exceeds 1 mol part, if the amount is close to 1 mol part, ZnS as a by-product of the above-described Zn system, etc. As a by-product of the formation of CaO, the formation of ZnS is suppressed as it approaches 1.5 mole parts. Further, when the amount exceeds 1.5 mol parts, an increase in CaO produced as a by-product is gradually observed.
ただし、焼成物中に含まれるCaOについては、例えば酸液等によって焼成物を洗浄することにより除去することができ、焼成物中におけるCaZnOS相の量を高めることも可能である。 However, CaO contained in the fired product can be removed by washing the fired product with an acid solution, for example, and the amount of CaZnOS phase in the fired product can be increased.
これらのような経験上、カルシウム化合物の量は１モル部以上の量が良く、好ましくは１モル部を超える量、より好ましくは１モル部を超え3モル部以下の量、更に好ましくは1.5±0.3モル部の範囲内の量とすることができる。特に、3モル部を越える量であっても酸液等による焼成物の洗浄を行うことでCaZnOS相の量を高めることはできるものの、過度に余剰な場合には洗浄効率の問題や洗浄コスト等の問題も生じるおそれがあるため、製造上においてはやや不利であるかもしれない。 Based on these experiences, the amount of the calcium compound is preferably 1 mol part or more, preferably more than 1 mol part, more preferably more than 1 mol part and 3 mol parts or less, still more preferably 1.5 ±. The amount can be in the range of 0.3 mole part. In particular, although the amount of CaZnOS phase can be increased by washing the fired product with an acid solution or the like even if the amount exceeds 3 mole parts, if it is excessive, problems with washing efficiency, washing costs, etc. May also be disadvantageous in manufacturing.
このようにカルシウムを過剰量添加することで、前述のZn系の副産物についてもCaと十分に反応させてCaZnOSを形成させることができるため、CaZnOSの生成効率を飛躍的に向上させることができる。なお、カルシウムの過剰量添加や、カルシウムを過剰量添加した場合の酸液等による焼成物の洗浄は必要に応じて行われるものであり、応力消光材料としての本来の機能を発揮可能であれば、これら不純物（副生成物）の濃度等に拘わらず、本発明の概念に含まれるものと解釈すべきである。ただし、上述のカルシウム添加量等の点で本発明を限定することを妨げるものではない。 By adding an excessive amount of calcium in this manner, the Zn-based by-product described above can be sufficiently reacted with Ca to form CaZnOS, so that the CaZnOS generation efficiency can be dramatically improved. In addition, the addition of an excessive amount of calcium and the cleaning of the fired product with an acid solution when an excessive amount of calcium is added are performed as necessary, so long as the original function as a stress quenching material can be exhibited. Regardless of the concentration of these impurities (by-products), it should be construed as being included in the concept of the present invention. However, it does not prevent the present invention from being limited in terms of the above-described calcium addition amount and the like.
また、本実施形態に係る応力消光材料の製造方法において亜鉛化合物は、好ましくは１モル部使用する。このときの許容される誤差は、±10mol%、すなわち、1±0.1モル部である。 Moreover, in the manufacturing method of the stress-quenching material which concerns on this embodiment, Preferably 1 mol part of zinc compounds are used. The allowable error at this time is ± 10 mol%, that is, 1 ± 0.1 mol part.
また、本実施形態に係る応力消光材料の製造方法において硫黄化合物は、好ましくは１モル部使用する。このときの許容される誤差は、±10mol%、すなわち、1±0.1モル部である。 Moreover, in the manufacturing method of the stress-quenching material which concerns on this embodiment, Preferably 1 mol part of sulfur compounds are used. The allowable error at this time is ± 10 mol%, that is, 1 ± 0.1 mol part.
また、本実施形態に係る応力消光材料の製造方法において銅化合物は、前記亜鉛化合物に含まれる亜鉛量の0.005〜8mol%に相当する銅を含有する量を使用する。具体的には、0.00005モル部以上、0.08モル部以下の量の銅を含有する銅化合物を使用する。 In the method for producing a stress-quenching material according to the present embodiment, the copper compound is used in an amount containing copper corresponding to 0.005 to 8 mol% of the zinc amount contained in the zinc compound. Specifically, a copper compound containing 0.00005 mol part or more and 0.08 mol part or less of copper is used.
そして、これらの各化合物を混合し、混合物を得る。混合の方法としては、例えば小規模の製造であれば、少量のエタノールなどの溶媒の存在下で、乳鉢などを用いて湿式混合し、その後溶媒を揮発させて乾燥させることにより混合物を得ることができる。また、大規模な製造であっても、これに準じた方法で公知の製造装置等を用いて製造することができる。 And each of these compounds is mixed and a mixture is obtained. As a mixing method, for example, in the case of small-scale production, wet mixing is performed using a mortar in the presence of a small amount of a solvent such as ethanol, and then the solvent is volatilized and dried to obtain a mixture. it can. Moreover, even if it is large-scale manufacture, it can manufacture using a well-known manufacturing apparatus etc. by the method according to this.
焼成工程では、このように調製した混合物を焼成する。焼成の方法としては、例えば小規模の製造であれば、得られた混合物をるつぼ等に収容し、加熱炉にて不活性ガス雰囲気下で加熱することで行うことができる。なお、このときの加熱温度は、1100±100℃であるのが好ましい。また、加熱時間としては、例えば、0.1〜100時間、好ましくは１〜12時間、より好ましくは５±３時間とすることができる。 In the firing step, the mixture thus prepared is fired. As a firing method, for example, in the case of small-scale production, the obtained mixture can be stored in a crucible or the like and heated in an inert gas atmosphere in a heating furnace. The heating temperature at this time is preferably 1100 ± 100 ° C. The heating time can be, for example, 0.1 to 100 hours, preferably 1 to 12 hours, and more preferably 5 ± 3 hours.
こうして得られた焼成物は、Cuイオンが固溶したCaZnOSの結晶体を含んでおり、加熱炉から取り出して冷却することにより（冷却工程）、応力消光材料となる。 The fired product thus obtained contains a CaZnOS crystal in which Cu ions are dissolved, and is taken out of the heating furnace and cooled (cooling step) to become a stress quenching material.
このように、本実施形態に係る応力消光材料の製造方法によれば、応力を付与することにより消光や減光を示す応力消光材料を製造可能な方法を提供することができる。 Thus, according to the manufacturing method of the stress-quenching material which concerns on this embodiment, the method which can manufacture the stress-quenching material which shows quenching | extinction and a light-extinction by providing stress can be provided.
付言すれば、本実施形態に係る応力消光材料の製造方法は、カルシウムを含有するカルシウム化合物の粉末と、亜鉛を含有する亜鉛化合物の粉末と、硫黄を含有する硫黄化合物の粉末と、銅を含有する銅化合物の粉末とを混合して混合物を得る工程と、前記混合物を焼成することにより、Cuイオンが固溶したCaZnOSの結晶体であって前記Cuイオンが前記CaZnOS中に含まれるZnの0.005〜8mol%に相当する濃度で固溶した結晶体を含む焼成物を生成する工程と、前記焼成物を冷却して応力消光材料を生成する冷却工程と、を有することを特徴とする応力消光材料の製造方法であるとも言える。また、Cuイオンが固溶したCaZnOSの結晶体においてCuイオンは、CaZnOS中に含まれるZnの0.005〜8mol%を置換する濃度で固溶していても良い。 If it adds, the manufacturing method of the stress-quenching material which concerns on this embodiment contains the powder of the calcium compound containing calcium, the powder of the zinc compound containing zinc, the powder of the sulfur compound containing sulfur, and copper A step of mixing a copper compound powder to obtain a mixture, and calcining the mixture to form a CaZnOS crystal in which Cu ions are solid solution, and the Cu ions are contained in the CaZnOS 0.005 A stress quenching material comprising: a step of producing a fired product containing crystallized solid solutions at a concentration corresponding to ˜8 mol%; and a cooling step of cooling the fired product to produce a stress quenching material. It can be said that this is a manufacturing method. In addition, in the crystal of CaZnOS in which Cu ions are dissolved, Cu ions may be dissolved in a concentration that substitutes 0.005 to 8 mol% of Zn contained in CaZnOS.
また、本実施形態に係る応力消光材料は、応力を付与することにより消光や減光を示すものであることから、この消光や減光を検出することにより、所定の部材に付与された応力の検出に使用することができる。 In addition, since the stress quenching material according to the present embodiment exhibits quenching or dimming by applying stress, the stress applied to a predetermined member can be detected by detecting this quenching or dimming. Can be used for detection.
以下、本実施形態に係る応力消光材料、及び応力消光体、並びに応力消光材料の製造方法について、各種試験データ等を参照しながら詳説する。 Hereinafter, the stress-quenching material, the stress-quenching material, and the method for producing the stress-quenching material according to the present embodiment will be described in detail with reference to various test data.
〔１．応力消光材料の作製〕
ここではまず、本実施形態に係る応力消光材料の製造方法について説明する。図２は本実施形態に係る応力消光材料の製造方法を示したフローである。
[1. (Manufacture of stress quenching material)
Here, the manufacturing method of the stress-quenching material which concerns on this embodiment is demonstrated first. FIG. 2 is a flow showing a method for manufacturing the stress-quenching material according to this embodiment.
図２に示すように、本実施形態に係る応力消光材料の製造方法では、まず、カルシウム化合物の粉末と、亜鉛化合物の粉末と、硫黄化合物の粉末と、銅化合物の粉末とを混合して混合物を得る混合工程を行う（ステップＳ１０）。 As shown in FIG. 2, in the method for manufacturing a stress quenching material according to this embodiment, first, a calcium compound powder, a zinc compound powder, a sulfur compound powder, and a copper compound powder are mixed and mixed. A mixing step is performed to obtain (Step S10).
具体的には、カルシウム化合物としてCaCO3を用い、1.5モル部に相当するカルシウムが含まれる量を量り取った。また、亜鉛化合物及び硫黄化合物としてはZnSを用い、１モル部に相当する亜鉛及び硫黄が含まれる量を量り取った。また、銅化合物としてはCu2Oを用い、0.0005モル部に相当する銅が含まれる量を量り取った。 Specifically, CaCO 3 was used as the calcium compound, and an amount containing calcium corresponding to 1.5 mol parts was measured. Moreover, ZnS was used as a zinc compound and a sulfur compound, and the amount of zinc and sulfur corresponding to 1 mol part was measured. Moreover, Cu 2 O was used as the copper compound, and the amount containing copper corresponding to 0.0005 mol part was weighed.
そして、それぞれ所定量ずつ秤量した粉体に少量のエタノールを加えてメノウ乳鉢で湿式混合し、エタノールを揮発させて乾燥した混合物を得ることで混合工程を行った。 Then, a small amount of ethanol was added to each of the powders weighed in predetermined amounts, wet mixed in an agate mortar, and the mixing step was performed by volatilizing ethanol to obtain a dried mixture.
次に、得られた混合物をアルミナ製のるつぼに収容し、加熱炉でアルゴン雰囲気下にて1100℃で５時間加熱する焼成工程を行い、焼成物を得た（ステップＳ２０）。 Next, the obtained mixture was accommodated in an alumina crucible and subjected to a firing step of heating at 1100 ° C. in an argon atmosphere for 5 hours in a heating furnace to obtain a fired product (step S20).
そして、得られた焼成物を加熱炉より取出し、大気中にて放冷することで（冷却工程・ステップＳ３０）、本実施形態に係る応力消光材料を得た。なお、必要に応じて、酢酸水溶液等により洗浄を行い、余剰のカルシウム分を除去するようにしても良い。 Then, the obtained fired product was taken out from the heating furnace and allowed to cool in the atmosphere (cooling step / step S30), thereby obtaining a stress quenching material according to the present embodiment. If necessary, the excess calcium content may be removed by washing with an acetic acid aqueous solution or the like.
〔２．応力消光体の調製〕
次に、後述する応力付与試験に供すべく、本実施形態に係る応力消光材料を用いて、応力消光体の調製を行った。
[2. Preparation of stress quencher
Next, a stress quencher was prepared using the stress quencher material according to the present embodiment in order to be subjected to a stress application test described later.
具体的には、応力消光材料（CaZn0.9995Cu0.0005OS）をマトリクス材料としてのエポキシ樹脂に添加し、硬化させて円柱状（直径25mm、厚み15mm）のペレットを形成した。 Specifically, a stress-quenching material (CaZn 0.9995 Cu 0.0005 OS) was added to an epoxy resin as a matrix material and cured to form a cylindrical pellet (diameter 25 mm, thickness 15 mm).
また、同様に応力消光材料（CaZn0.9995Cu0.0005OS）をマトリクス材料としてのエポキシ樹脂に添加し、硬化させてシート体（縦10mm×横10mm×厚さ0.08mm）を形成した。これらはいずれも、本実施形態に係る応力消光体として以下の実験に用いた。 Similarly, a stress-quenching material (CaZn 0.9995 Cu 0.0005 OS) was added to the epoxy resin as a matrix material and cured to form a sheet (length 10 mm × width 10 mm × thickness 0.08 mm). All of these were used in the following experiments as stress quenchers according to the present embodiment.
〔３．荷重印加試験〕
次に、前述のペレットを用い、荷重を付与してMQ現象を確認する試験を行った。具体的には、ペレットをテンシロン万能材料試験機（株式会社オリエンテック製 RTC-1310A）に供し0〜1000Nまでの圧縮応力を付与することで、ペレットから放射される蛍光の強度を測定した。
[3. (Load application test)
Next, a test was performed to confirm the MQ phenomenon by applying a load using the above-described pellets. Specifically, the intensity of fluorescence emitted from the pellet was measured by applying the pellet to a Tensilon universal material testing machine (RTC-1310A manufactured by Orientec Co., Ltd.) and applying a compressive stress of 0 to 1000 N.
なお、ペレットは試験前に紫外線ランプを用いて365nmの紫外光を励起光として１分間照射し、照射終了１分後から試験を開始した。また、蛍光強度は、光電子増倍管（浜松ホトニクス株式会社製 R585S）と、フォトン計数器（浜松ホトニクス株式会社製 C5410-51）と、コンピュータとにより構成されたフォトン計数システムにより測定した。その結果を図３及び図４に示す。 The pellets were irradiated for 1 minute using 365 nm ultraviolet light as excitation light using an ultraviolet lamp before the test, and the test was started 1 minute after the end of irradiation. The fluorescence intensity was measured by a photon counting system composed of a photomultiplier tube (R585S manufactured by Hamamatsu Photonics Co., Ltd.), a photon counter (C5410-51 manufactured by Hamamatsu Photonics Co., Ltd.), and a computer. The results are shown in FIGS.
図３は蛍光強度の経時変化を示したグラフであり、左縦軸は蛍光強度、右縦軸は荷重、横軸は時間を示しており、また、白丸は荷重を付与しない場合の蛍光強度、黒丸は荷重を付与した場合の蛍光強度、実線は荷重の経時変化を示している。 FIG. 3 is a graph showing changes in fluorescence intensity over time, the left vertical axis shows the fluorescence intensity, the right vertical axis shows the load, the horizontal axis shows the time, and the white circle shows the fluorescence intensity when no load is applied, A black circle indicates the fluorescence intensity when a load is applied, and a solid line indicates a change with time of the load.
図３からも分かるように、本実施形態に係る応力消光体（応力消光材料）は、応力の付与に応じて蛍光強度が減衰（消光）することが示された。 As can be seen from FIG. 3, the stress quencher (stress quenching material) according to the present embodiment was shown to attenuate (quenching) the fluorescence intensity in response to the application of stress.
図４は、応力と消光強度との関係を示したグラフであり、縦軸に消光強度、横軸に荷重を示している。図４からも分かるように、本実施形態に係る応力消光体（応力消光材料）は、応力の大きさに応じて消光強度が高まることが確認された。 FIG. 4 is a graph showing the relationship between the stress and the extinction intensity, with the vertical axis indicating the extinction intensity and the horizontal axis indicating the load. As can be seen from FIG. 4, it was confirmed that the stress quencher (stress quenching material) according to the present embodiment increases the quenching intensity according to the magnitude of the stress.
〔４．引張試験〕
次に、前述のシート体を用い、引張荷重を付与してMQ現象を確認する試験を行った。具体的には、長さ150mm×幅20mm×厚さ3mmのアルミニウム合金製のプレート表面にシート体を貼着すると共に、裏面にひずみゲージ（株式会社共和電業製 KFG-2-120-C1-11L1M2R）を取付け、テンシロン万能材料試験機（株式会社オリエンテック製 RTC-1310A）に供して引張応力を付与することで、シート体から放射される蛍光の強度を測定した。
[4. Tensile test)
Next, a test for confirming the MQ phenomenon by applying a tensile load was performed using the above-described sheet body. Specifically, a sheet body is attached to the surface of an aluminum alloy plate 150 mm long x 20 mm wide x 3 mm thick, and a strain gauge (KFG-2-120-C1- 11L1M2R) was attached and subjected to a Tensilon universal material testing machine (RTC-1310A manufactured by Orientec Co., Ltd.) to apply tensile stress, thereby measuring the intensity of fluorescence emitted from the sheet body.
なお、シート体は試験前に紫外線ランプを用いて365nmの紫外光を励起光として１分間照射し、照射終了１分後から試験を開始した。また、蛍光は、CCDカメラにて撮像した画像を解析することにより強度の算出を行った。その結果を図５に示す。 Before the test, the sheet body was irradiated with 365 nm ultraviolet light as excitation light for 1 minute using an ultraviolet lamp, and the test was started 1 minute after the end of irradiation. In addition, the intensity of fluorescence was calculated by analyzing an image captured by a CCD camera. The result is shown in FIG.
図５は試験材料の伸びと消光強度との関係を示したグラフであり、縦軸が消光強度、横軸が伸びを示している。図５からも分かるように、本実施形態に係る応力消光体（応力消光材料）は、変形割合に応じた減光（消光）を示すことが確認された。 FIG. 5 is a graph showing the relationship between the elongation of the test material and the extinction intensity. The vertical axis represents the extinction intensity and the horizontal axis represents the elongation. As can be seen from FIG. 5, it was confirmed that the stress quencher (stress quenching material) according to the present embodiment exhibits dimming (quenching) according to the deformation ratio.
上述した〔３．荷重印加試験〕や〔４．引張試験〕の試験結果から、本実施形態に係る応力消光材料や応力消光体は、応力を受けることにより蛍光が減衰または消光することが示された。 As described above [3. Load application test] and [4. From the test results of [Tensile test], it was shown that the stress-quenching material and the stress-quenching material according to the present embodiment attenuate or quench the fluorescence when subjected to stress.
〔５．Cuの濃度依存性の検証〕
次に、母体材料中に存在するCuの濃度を変えることにより、消光強度がどのように変化するかについて検討を行った。
[5. (Verification of Cu concentration dependence)
Next, we examined how the extinction intensity changes by changing the concentration of Cu present in the base material.
具体的には、CaZnOS中に含まれるZnの0.005mol%に相当する濃度でCuイオンを固溶させたCaZn0.99995Cu0.00005OS、0.01mol%に相当する濃度で固溶させたCaZn0.9999Cu0.0001OS、0.05mol%に相当する濃度で固溶させたCaZn0.9995Cu0.0005OS、0.1mol%に相当する濃度で固溶させたCaZn0.999Cu0.001OS、0.2mol%に相当する濃度で固溶させたCaZn0.998Cu0.002OS、0.4mol%に相当する濃度で固溶させたCaZn0.996Cu0.004OS、2mol%に相当する濃度で固溶させたCaZn0.98Cu0.02OS、4mol%に相当する濃度で固溶させたCaZn0.96Cu0.04OS、6mol%に相当する濃度で固溶させたCaZn0.94Cu0.06OS、8mol%に相当する濃度で固溶させたCaZn0.92Cu0.08OSを調製し、前述の〔２．応力消光体の調製〕で述べた方法と同様の方法でペレットをそれぞれ作成した。 Specifically, CaZn 0.99995 Cu 0.00005 OS in which Cu ions are dissolved at a concentration corresponding to 0.005 mol% of Zn contained in CaZnOS , CaZn 0.9999 Cu 0.0001 OS in a concentration corresponding to 0.01 mol% CaZn 0.9995 Cu 0.0005 OS dissolved at a concentration equivalent to 0.05 mol%, CaZn 0.999 Cu 0.001 OS dissolved at a concentration equivalent to 0.1 mol%, CaZn dissolved at a concentration equivalent to 0.2 mol% 0.998 Cu 0.002 OS, CaZn dissolved at a concentration equivalent to 0.4 mol% 0.996 Cu 0.004 OS, dissolved at a concentration equivalent to 2 mol% CaZn 0.98 Cu 0.02 OS, dissolved at a concentration equivalent to 4 mol% CaZn 0.96 Cu 0.04 OS, CaZn 0.94 Cu 0.06 OS dissolved at a concentration corresponding to 6 mol%, and CaZn 0.92 Cu 0.08 OS dissolved at a concentration corresponding to 8 mol% were prepared, and the above-mentioned [2. Pellets were prepared by the same method as described in [Preparation of stress quencher].
次いで、作成した10種類のペレットについて、前述の〔３．荷重印加試験〕と同様の試験を行い、1000N印加時の消光強度を測定した。その結果を図６に示す。 Subsequently, about the produced 10 types of pellets, [3. The same test as in [Load application test] was performed, and the quenching intensity when 1000 N was applied was measured. The result is shown in FIG.
図６は、応力消光材料中のCuの濃度と消光強度との関係を示したグラフであり、縦軸に消光強度、横軸にCu濃度を示している。図６からも分かるように、CaZn0.99995Cu0.00005OSで17276であった消光強度は、CaZn0.9999Cu0.0001OSで85473とピークに達し、CaZn0.9995Cu0.0005OSで55708、CaZn0.999Cu0.001OSで21949、CaZn0.998Cu0.002OSで19079、CaZn0.996Cu0.004OSで14757と順次低下傾向を見せた。 FIG. 6 is a graph showing the relationship between the Cu concentration and the quenching intensity in the stress quenching material, where the vertical axis represents the quenching intensity and the horizontal axis represents the Cu concentration. As can be seen from FIG. 6, the extinction intensity of 17276 in CaZn 0.99995 Cu 0.00005 OS reached a peak of 85473 in CaZn 0.9999 Cu 0.0001 OS, 55708 in CaZn 0.9995 Cu 0.0005 OS, 21949 in CaZn 0.999 Cu 0.001 OS. The CaZn 0.998 Cu 0.002 OS showed 19079 and the CaZn 0.996 Cu 0.004 OS showed 14757 and showed a downward trend.
また、Cu濃度を更に増加させると、CaZn0.98Cu0.02OSで2684、CaZn0.96Cu0.04OSで2256、CaZn0.94Cu0.06OSで1194となり、CaZn0.92Cu0.08OSで1004と消光強度は更に低下した。なお、図示は割愛するが、CaZnOS中に含まれるZnの0.001mol%に相当する濃度でCuイオンを固溶させたCaZn0.99999Cu0.00001OSや、Cuイオンを固溶させていない母体材料であるCaZnOSではMQ現象は観察されず、mechanoluminescence（発光現象、応力発光）だけが観察された。また、CaZnOS中に含まれるZnの12mol%に相当する濃度でCuイオンを固溶させたCaZn0.88Cu0.12OSにおいても、MQ現象は観察されなかった。 Further, when the Cu concentration was further increased, the quenching intensity decreased further to 2684 for CaZn 0.98 Cu 0.02 OS, 2256 for CaZn 0.96 Cu 0.04 OS, and 1194 for CaZn 0.94 Cu 0.06 OS, and 1004 for CaZn 0.92 Cu 0.08 OS. Although illustration is omitted, CaZn 0.99999 Cu 0.00001 OS in which Cu ions are dissolved at a concentration corresponding to 0.001 mol% of Zn contained in CaZnOS, and CaZnOS which is a base material in which Cu ions are not dissolved. However, MQ phenomenon was not observed, and only mechanoluminescence (luminescence phenomenon, stress luminescence) was observed. In addition, no MQ phenomenon was observed in CaZn 0.88 Cu 0.12 OS in which Cu ions were dissolved at a concentration corresponding to 12 mol% of Zn contained in CaZnOS.
これらの結果から、母体材料であるCaZnOS中に固溶させるCuイオンの濃度は、CaZnOS中に含まれるZnの0.005〜8mol%とすることで、特に顕著なMQ現象を生起可能な応力消光材料が得られることが示された。 From these results, the concentration of Cu ions to be dissolved in the base material CaZnOS is set to 0.005 to 8 mol% of Zn contained in CaZnOS. It was shown to be obtained.
上述してきたように、本実施形態に係る応力消光材料によれば、Cuイオンが固溶したCaZnOSの結晶体を含有することとしたため、応力を受けることにより蛍光が減衰または消光する応力消光材料を提供することができる。 As described above, according to the stress-quenching material according to the present embodiment, since the Cu ions are included in the CaZnOS crystal, the stress-quenching material in which the fluorescence is attenuated or quenched by receiving the stress. Can be provided.
最後に、上述した各実施の形態の説明は本発明の一例であり、本発明は上述の実施の形態に限定されることはない。このため、上述した各実施の形態以外であっても、本発明に係る技術的思想を逸脱しない範囲であれば、設計等に応じて種々の変更が可能であることは勿論である。 Finally, the description of each embodiment described above is an example of the present invention, and the present invention is not limited to the above-described embodiment. For this reason, it is a matter of course that various modifications can be made in accordance with the design and the like as long as they do not depart from the technical idea according to the present invention other than the embodiments described above.
Claims (7)
応力の付与により前記第１のトラップ準位のキャリアが遷移する第２のトラップ準位有し、付与された応力に応じて前記第１のトラップ準位から前記安定準位へ遷移可能なキャリア数を減ずることにより消光を示すべく構成したことを特徴とする応力消光材料。 In a material that emits light by energy of a difference when carriers in an excited state trapped in the first trap level transition to a stable level lower than the first trap level,
The number of carriers having a second trap level in which carriers of the first trap level transition by application of stress and capable of transitioning from the first trap level to the stable level in accordance with the applied stress A stress quenching material configured to exhibit quenching by reducing.
前記混合物を焼成することによりCuイオンが固溶したCaZnOSの結晶体を含む焼成物を生成する工程と、
前記焼成物を冷却して応力消光材料を生成する冷却工程と、
を有することを特徴とする応力消光材料の製造方法。 A powder of calcium compound containing 1 to 3 mole parts of calcium, a powder of zinc compound containing 1 ± 0.1 mole parts of zinc, a powder of sulfur compound containing 1 ± 0.1 mole parts of sulfur, and the zinc A step of mixing a copper compound powder containing copper corresponding to 0.005 to 8 mol% of the amount of zinc contained in the compound to obtain a mixture;
Producing a fired product containing CaZnOS crystals in which Cu ions are dissolved by firing the mixture; and
A cooling step of cooling the fired product to produce a stress-quenching material;
A method for producing a stress-quenching material, comprising:
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