TWI728158B - Hydrogen-containing liquid, method for manufacturing hydrogen-containing liquid, apparatus for manufacturing hydrogen-containing liquid, and biological hydrogen generating material - Google Patents
Hydrogen-containing liquid, method for manufacturing hydrogen-containing liquid, apparatus for manufacturing hydrogen-containing liquid, and biological hydrogen generating material Download PDFInfo
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Abstract
Description
本發明係有關一種含氫溶液、含氫溶液的製造方法、及含氫溶液的製造裝置、或富氫水、富氫水的製造方法、及富氫水的製造裝置、與活體用氫生成材料。The present invention relates to a hydrogen-containing solution, a hydrogen-containing solution manufacturing method, and a hydrogen-containing solution manufacturing device, or a hydrogen-rich water, a hydrogen-rich water manufacturing method, and a hydrogen-rich water manufacturing device, and a hydrogen generating material for living organisms .
使氫溶解於水中而得到的富氫水必需具有1ppm以上的溶解氫濃度。由於藉由利用富氫水可以除去活性氧，因此在健康飲用水、洗臉水、入浴水、醫療領域或電子元件的洗淨水、或植物的促進生長水等多方面的利用都逐步進行中。一般而言，作為富氫水的製造技術或製造裝置，係藉由將氫氣體導入水中，或是進行水的電解法（例如，專利文獻1）。The hydrogen-rich water obtained by dissolving hydrogen in water must have a dissolved hydrogen concentration of 1 ppm or more. Since the active oxygen can be removed by the use of hydrogen-rich water, the use of healthy drinking water, face wash, bath water, medical field or electronic component washing water, or plant growth promotion water, etc. are gradually being used. Generally speaking, as a hydrogen-rich water production technology or production device, hydrogen gas is introduced into water or water electrolysis is performed (for example, Patent Document 1).
此外，本發明人針對藉由矽奈米粒子之水的分解與氫濃度做了研究，並公開其結果（非專利文獻1、專利文獻2）。In addition, the present inventors conducted research on the decomposition of water and hydrogen concentration by silicon nanoparticles, and disclosed the results (Non-Patent Document 1 and Patent Document 2).
現有技術文獻Prior art literature
專利文獻Patent literature
專利文獻1：日本特開第2006-95389號公報 專利文獻2：日本特開第2016-155118號公報Patent Document 1: Japanese Patent Application Publication No. 2006-95389 Patent Document 2: Japanese Patent Application Publication No. 2016-155118
非專利文獻Non-patent literature
非專利文獻1：松田真輔等，藉由矽奈米粒子之水的分解與氫濃度，第62次應用物理學會春季學術演講會 演講預印本，2015，11a-A27-6Non-Patent Document 1: Matsuda Shinsuke et al., The 62nd Spring Academic Lecture of the Society of Applied Physics Lecture Preprint, 2015, 11a-A27-6, by the decomposition of water and hydrogen concentration of silicon nanoparticles
發明要解決之課題Problems to be solved by the invention
然而，在專利文獻1所揭露的富氫水的製造技術中，需要直接導入氫氣體的過程，其控制及處理上有問題。此外，目前市場需求為使用低成本且對活體及活體內的安全性高的氫生成材料、就地（on site）簡便的富氫水、其製造方法及其製造裝置。However, in the hydrogen-rich water manufacturing technology disclosed in Patent Document 1, a process of directly introducing hydrogen gas is required, and there are problems in its control and processing. In addition, the current market demand is the use of low-cost and high-safety hydrogen-generating materials for living bodies and living bodies, simple on-site hydrogen-rich water, its manufacturing method and its manufacturing device.
本發明解決至少一個上述技術問題，有效利用微小的矽粒子，藉由meb具有優異的安全性、經濟性、及工業性的製造方法生成氫，對於簡單且安全的含氫溶液、含氫溶液的製造方法、及含氫溶液的製造裝置、或富氫水、富氫水的製造方法、及富氫水的製造裝置的實現作出大的貢獻。The present invention solves at least one of the above-mentioned technical problems, effectively utilizes tiny silicon particles, and generates hydrogen through meb's excellent safety, economy, and industrial manufacturing method. It is suitable for simple and safe hydrogen-containing solutions and hydrogen-containing solutions. The manufacturing method and the hydrogen-containing solution manufacturing device, or the hydrogen-rich water, the hydrogen-rich water manufacturing method, and the hydrogen-rich water manufacturing device have made a great contribution to the realization.
本發明人注目於半導體或發光元件中矽微小粒子的有效利用而進行了研究。另一方面，針對從所述矽微小粒子製造具有優異的實用性及工業性的氫的技術，做了深入研究。其結果為，發現了即使在室溫之溫和的條件下，將低成本且安全的材料的微小矽粒子分散於水中，可以從水中生成氫，並發現使氫溶解於水中，可以實現具有受控制的氫濃度的富氫水。The inventors of the present invention paid attention to the effective use of silicon fine particles in semiconductors or light-emitting devices and conducted research. On the other hand, in-depth research has been conducted on the technology of producing hydrogen with excellent practicality and industriality from the silicon microparticles. As a result, it was discovered that even under mild conditions at room temperature, dispersing low-cost and safe material of micro silicon particles in water can generate hydrogen from water, and found that hydrogen can be dissolved in water to achieve controlled The hydrogen-rich water with the highest hydrogen concentration.
本發明係基於上述觀點而創作者。The present invention was created based on the above viewpoint.
本發明之一種含氫溶液係將藉由矽微小奈米粒子及/或該矽微小奈米粒子的凝聚體與水或水溶液接觸所生成的氫溶解在上述水或上述水溶液之中，其中矽微小奈米粒子及/或上述凝聚體係在乙醇中將矽微小粒子粉碎並使得到的矽微小奈米粒子及/或該上述凝聚體與過氧化氫溶液接觸。The hydrogen-containing solution of the present invention dissolves the hydrogen generated by the contact of silicon micro-nanoparticles and/or the agglomerates of the silicon micro-nanoparticles with water or aqueous solution in the water or the aqueous solution, wherein the silicon micro-nanoparticles The nano particles and/or the agglomerate system pulverize the silicon fine particles in ethanol, and the obtained silicon fine nano particles and/or the agglomerate are brought into contact with the hydrogen peroxide solution.
又，本發明之一種活體用氫生成材料包含：使在乙醇中將矽微小粒子粉碎所得到的矽微小奈米粒子及/或該矽微小奈米粒子的凝聚體與過氧化氫溶液接觸的上述矽微小奈米粒子及/或上述凝聚體。In addition, a hydrogen generating material for living organisms of the present invention includes: the above-mentioned silicon micro-nanoparticles obtained by pulverizing silicon micro-particles in ethanol and/or an aggregate of the silicon micro-nanoparticles are contacted with a hydrogen peroxide solution Silicon micro-nanoparticles and/or agglomerates mentioned above.
又，本發明之一種含氫溶液的製造方法包含以下各工序：藉由在乙醇中將矽微小粒子粉碎以形成矽微小奈米粒子及/或該矽微小奈米粒子的凝聚體的工序；過氧化氫溶液處理工序，使上述矽微小奈米粒子及/或上述凝聚體與過氧化氫溶液接觸；及溶解工序，在上述過氧化氫溶液處理工序之後，將藉由使上述矽微小奈米粒子及/或上述凝聚體與水或水溶液接觸而生成的氫溶解在上述水或上述水溶液之中。In addition, a method for producing a hydrogen-containing solution of the present invention includes the following steps: a step of pulverizing silicon microparticles in ethanol to form silicon microparticles and/or an aggregate of the silicon microparticles; The hydrogen oxide solution treatment step is to contact the silicon micro-nanoparticles and/or the agglomerates with hydrogen peroxide solution; and the dissolution step, after the hydrogen peroxide solution treatment step, the silicon micro-nanoparticles And/or the hydrogen produced by contacting the agglomerates with water or an aqueous solution is dissolved in the water or the aqueous solution.
又，本發明之一種含氫溶液的製造裝置具有：粉碎部，藉由在乙醇中將矽微小粒子粉碎以形成矽微小奈米粒子及/或該矽微小奈米粒子的凝聚體；過氧化氫溶液處理部，使上述矽微小奈米粒子及/或上述凝聚體與過氧化氫溶液接觸；及溶解處理部，將藉由使與上述過氧化氫溶液接觸的上述矽微小奈米粒子及/或上述凝聚體與水或水溶液接觸所生成的氫溶解在上述水或上述水溶液之中。In addition, a hydrogen-containing solution manufacturing apparatus of the present invention has: a pulverizing section for pulverizing silicon micro-particles in ethanol to form silicon micro-nanoparticles and/or an aggregate of the silicon micro-nanoparticles; hydrogen peroxide The solution treatment part brings the silicon micro-nanoparticles and/or the agglomerates into contact with a hydrogen peroxide solution; and the dissolution treatment part brings the silicon micro-nanoparticles and/or the hydrogen peroxide solution into contact with each other. The hydrogen generated by the contact of the agglomerate with water or an aqueous solution is dissolved in the water or the aqueous solution.
又，本發明之一種富氫水，其中使矽微小粒子、或者將上述矽微小粒子進一步粉碎的矽微小粒子（以下稱為「矽微小奈米粒子」）及/或該矽微小奈米粒子的凝聚體接觸及/或分散於水中以生成氫，且使上述氫直接溶解在上述水中並密封在容器中。In addition, a hydrogen-rich water of the present invention, wherein silicon fine particles, or silicon fine particles obtained by further pulverizing the above-mentioned silicon fine particles (hereinafter referred to as "silicon fine nanoparticles") and/or silicon fine nanoparticles The agglomerates are contacted and/or dispersed in water to generate hydrogen, and the hydrogen is directly dissolved in the water and sealed in a container.
本發明之一種富氫水的製造裝置包含：粉碎部，用以形成矽微小粒子或將上述矽微小粒子進一步粉碎的矽微小奈米粒子；及富氫水生成部，使上述矽微小奈米粒子及/或其凝聚體接觸或分散於水或水溶液內，以直接使氫溶解於上述水中並密封以製造富氫水。An apparatus for producing hydrogen-rich water of the present invention includes: a pulverizing section for forming silicon microparticles or silicon micronanoparticles for further pulverizing the silicon microparticles; and a hydrogen-rich water generating section for making the silicon micronanoparticles And/or its agglomerates are contacted or dispersed in water or an aqueous solution to directly dissolve hydrogen in the water and seal to produce hydrogen-rich water.
藉由此富氫水的製造裝置，使矽微小奈米粒子及/或其凝聚體在密封容器中接觸或者分散於水或水溶液中，可以高準確性、低成本、且安全地就地製造具有足夠實用性的氫濃度與量的富氫水。藉由此富氫水的製造裝置，可以大幅提高富氫水的製造之工業生產性。With this hydrogen-rich water manufacturing device, silicon micro-nanoparticles and/or their aggregates can be contacted in a sealed container or dispersed in water or aqueous solutions, which can be manufactured on-site with high accuracy, low cost, and safety. Sufficient practical hydrogen concentration and amount of hydrogen-rich water. With this hydrogen-rich water production device, the industrial productivity of hydrogen-rich water production can be greatly improved.
又，本發明之一種富氫水的製造方法包含：粉碎工序，形成矽微小粒子；及富氫水的生成工序，使矽微小奈米粒子及/或其凝聚體接觸或者分散於水或水溶液以生成氫，並使該氫溶解於該水中並密封。In addition, a method for producing hydrogen-rich water of the present invention includes: a pulverization step to form fine silicon particles; and a step of generating hydrogen-rich water, which involves contacting or dispersing silicon micro-nanoparticles and/or aggregates in water or an aqueous solution. Hydrogen is generated, and the hydrogen is dissolved in the water and sealed.
藉由此富氫水的製造方法，將矽微小粒子作為起始材料，可以製造具有足夠實用性的氫濃度與量的富氫水。又，此富氫水的製造方法不僅有效利用矽微小奈米粒子，對環境保護做出大的貢獻，也能做為飲用水等。藉由此富氫水的製造方法，可以大幅削減富氫水的製造成本，與大幅提高工業生產性。With this method for producing hydrogen-rich water, using silicon microparticles as a starting material, hydrogen-rich water with sufficient practical hydrogen concentration and amount can be produced. Moreover, this hydrogen-rich water production method not only effectively utilizes silicon micro-nanoparticles and makes a great contribution to environmental protection, but also can be used as drinking water. With this method for producing hydrogen-rich water, the production cost of hydrogen-rich water can be greatly reduced, and industrial productivity can be greatly improved.
又，在本發明之一種富氫水的製造中使用的矽微小奈米粒子及/或其凝聚體係微晶直徑的分佈為100nm（奈米）以下，較佳為50nm以下的範圍。採用此範圍適合於生成富氫水，即，在水中生成氫，使該氫溶解在該水中，並密封於容器中。In addition, the distribution of the crystallite diameter of the silicon micro-nanoparticles and/or its aggregated system used in the production of the hydrogen-rich water of the present invention is 100 nm (nanometers) or less, preferably 50 nm or less. Using this range is suitable for generating hydrogen-rich water, that is, generating hydrogen in the water, dissolving the hydrogen in the water, and sealing the container in the container.
此外，在矽微小奈米粒子之中，以進行過化學處理（代表性處理為後述之各實施形態中的藉由氟酸水溶液及/或氟化銨水溶液的氧化膜的除去處理）者為適合作為富氫水製造用矽微小奈米粒子的一例。又，本發明之一種富氫水的製造方法包含形成矽微小奈米粒子的粉碎工序。In addition, among the silicon micro-nanoparticles, a chemical treatment (representative treatment is the removal treatment of the oxide film by a hydrofluoric acid aqueous solution and/or an ammonium fluoride aqueous solution in each embodiment described later) is suitable. As an example of silicon micro-nanoparticles for the production of hydrogen-rich water. In addition, a method for producing hydrogen-rich water of the present invention includes a pulverization step of forming silicon micro-nanoparticles.
此外，在矽微小奈米粒子之中，以進行過化學處理（代表性的有後述之各實施形態中之藉由過氧化氫溶液的加熱處理）者為適合作為在活體及活體內的富氫水製造用矽微小奈米粒子的一例，本發明之一種含氫溶液或富氫水的製造方法為了形成矽微小奈米粒子，包含在乙醇中的粉碎工序。In addition, among the silicon micro-nanoparticles, those that have been chemically treated (typically, the heat treatment with hydrogen peroxide solution in each embodiment described later) is suitable as the hydrogen-rich in the living body and the living body. As an example of silicon micro-nanoparticles for water production, the method for producing a hydrogen-containing solution or hydrogen-rich water of the present invention includes a pulverization process in ethanol in order to form silicon micro-nanoparticles.
藉由上述富氫水製造用的矽微小奈米粒子及其製造方法，提供矽微小奈米粒子及/或其凝聚體，作為有效地製造具有足夠實用性的氫濃度與量的富氫水的具有活體安全性的材料。By using the above-mentioned silicon micro-nanoparticles for hydrogen-rich water production and its manufacturing method, silicon micro-nanoparticles and/or aggregates thereof are provided as an effective method for producing hydrogen-rich water with sufficient practical hydrogen concentration and amount. Material with in vivo safety.
發明效果Invention effect
藉由本發明之一種含氫溶液或富氫水的製造裝置、及本發明之一種含氫溶液或富氫水的製造方法，矽微小奈米粒子作為生成含氫溶液或富氫水的起始材料，被利用在高準確性、低成本、且安全地、就地製造具有足夠實用性的氫濃度與量的含氫溶液或富氫水。因此，可以有效利用矽微小奈米粒子及/或其凝聚體，不僅對環境保護或活體安全性做出貢獻，也對含氫溶液或富氫水的製造成本的大幅削減做出貢獻。With the hydrogen-containing solution or hydrogen-rich water manufacturing device of the present invention, and the hydrogen-containing solution or hydrogen-rich water manufacturing method of the present invention, silicon micro-nanoparticles are used as starting materials for generating hydrogen-containing solution or hydrogen-rich water , It is used to produce hydrogen-containing solution or hydrogen-rich water with sufficient practical hydrogen concentration and quantity with high accuracy, low cost, and safety, on-site. Therefore, silicon micro-nanoparticles and/or their aggregates can be effectively used, which not only contributes to environmental protection or living body safety, but also contributes to a significant reduction in the production cost of hydrogen-containing solutions or hydrogen-rich water.
[實施例1][Example 1]
基於添附的圖式詳細說明本發明之實施形態。The embodiments of the present invention will be described in detail based on the attached drawings.
本實施形態之矽微小粒子的一例為，市售的高純度矽粉末（也稱為「高純度Si粉末」）（例如，高純度化學研究所公司製造，粒度分佈＜φ5μm，純度99.9%，i型矽）。又，本實施形態之矽微小奈米粒子的一例為，以該高純度矽粉末作為起始材料，藉由珠磨法將該高純度矽粉末微小化。在密閉容器內，使矽微小粒子或矽微小奈米粒子與複數種類的水溶液接觸。此外，該水溶液之一例為混合了pH値為8的弱鹼性硼酸鉀緩衝溶液的水溶液，該水溶液的另一例為pH値為7的超純水。又，該水溶液的再另一例為pH値為7.1-7.3的標準自來水。在密閉容器內，使各水溶液分別接觸矽微小粒子或矽微小奈米粒子。An example of the silicon microparticles of this embodiment is a commercially available high-purity silicon powder (also called "high-purity Si powder") (for example, manufactured by High-Purity Chemical Research Institute, particle size distribution <φ5μm, purity 99.9%, i Type silicon). In addition, an example of the silicon micro-nanoparticles of the present embodiment is to use the high-purity silicon powder as a starting material to miniaturize the high-purity silicon powder by a bead milling method. In an airtight container, make silicon microparticles or silicon nanoparticle contact a plurality of types of aqueous solutions. In addition, an example of the aqueous solution is an aqueous solution mixed with a weakly alkaline potassium borate buffer solution having a pH value of 8, and another example of the aqueous solution is ultrapure water having a pH value of 7. In addition, yet another example of the aqueous solution is standard tap water with a pH value of 7.1-7.3. In a closed container, each aqueous solution is contacted with silicon microparticles or silicon nanoparticle.
此外，上述矽微小奈米粒子係，使用珠磨裝置（AIMEX股份公司製造:RMB型批式Ready研磨機），將高純度矽粉末15g分散到99%以上的異丙醇（IPA）300ml中，加入φ;0.5μm的氧化鋯製小珠（容量300ml），以旋轉數2500rpm進行粉碎（一階段粉碎）4小時。其結果為，藉由X光繞射裝置（XRD）的測量，得到平均微晶直徑（體積分佈）為20.0nm的矽微小奈米粒子。再使用φ;0.3mm的氧化鋯製小珠（容量300ml），對上述矽微小奈米粒子以旋轉數2500rpm進行粉碎（二階段粉碎）4小時，藉由XRD的測量，得到平均微晶直徑（體積分佈）為10.9nm的矽微小奈米粒子。In addition, the above-mentioned silicon micro-nanoparticle system uses a bead mill (manufactured by AIMEX Co., Ltd.: RMB-type batch-ready mill) to disperse 15 g of high-purity silicon powder into 300 ml of isopropyl alcohol (IPA) of 99% or more. Add φ; 0.5μm zirconia beads (capacity 300ml), and pulverize (one-stage pulverization) at 2500 rpm for 4 hours. As a result, by X-ray diffraction (XRD) measurement, silicon micro-nanoparticles with an average crystallite diameter (volume distribution) of 20.0 nm were obtained. Then use φ; 0.3mm zirconia beads (300ml in capacity) to pulverize the silicon micronanoparticles at a rotation speed of 2500rpm (two-stage pulverization) for 4 hours, and obtain the average crystallite diameter by XRD measurement ( Volume distribution) is 10.9nm silicon micronanoparticles.
圖1為顯示本實施例中之珠磨機的一階段粉碎工序後得到的矽微小奈米粒子的結晶結構例的斷面TEM（穿透式電子顯微鏡）照片。圖1顯示由於矽微小奈米粒子的一部分凝聚，而形成不定形的約0.5μm以下的稍大的微粒子的狀態。又，圖2係針對個別的矽微小奈米粒子擴大後的TEM照片。如圖2中以白線包圍的區域所示，可以確認約5nm至10nm的大小的矽微小奈米粒子。又，可以確認此矽微小奈米粒子具有結晶性（（111）面）。外觀為不定形的形狀，可見到一部分為矽微小奈米粒子的凝聚體。雖然未圖示，然而藉由二階段粉碎後的TEM照片的分析，得到具有一階段粉碎後的約1/2左右以下的結晶性（（111）面）的矽微小奈米粒子。FIG. 1 is a cross-sectional TEM (transmission electron microscope) photograph showing an example of the crystal structure of silicon micro-nanoparticles obtained after the one-stage pulverization process of the bead mill in this embodiment. Figure 1 shows a state where a part of the silicon micro-nanoparticles aggregates to form slightly larger particles of approximately 0.5 μm or less in an amorphous shape. In addition, Figure 2 is an enlarged TEM image of individual silicon micro-nanoparticles. As shown in the area surrounded by white lines in Fig. 2, fine silicon nanoparticles with a size of about 5 nm to 10 nm can be confirmed. In addition, it can be confirmed that the silicon micro-nanoparticles have crystallinity ((111) plane). The appearance is an indeterminate shape, and a part of it is agglomerates of silicon micro-nanoparticles. Although not shown, the analysis of the TEM photographs after the two-stage pulverization revealed that silicon micro-nanoparticles with crystallinity ((111) plane) less than about 1/2 of the one-stage pulverization were obtained.
圖3為顯示使用X光繞射裝置（股份公司Rigaku，產品名「SmartLab」）進行測量及分析，作為一階段粉碎之實施例的結果，所得到的矽微小奈米粒子的例子的微晶直徑分佈的結果的圖。在圖3中，横軸表示微晶直徑（nm），縱軸表示頻率。又，實線顯示個數分佈基準的微晶直徑分佈，虛線顯示體積分佈基準的微晶直徑分佈。在個數分佈中，模式直徑（Mode diameter）為0.29nm，中位直徑（Median diameter）（50%微晶直徑）為0.75nm，平均直徑為1.2nm。又，在體積分佈中，模式直徑為4.9nm，中位直徑為12.5nm，平均直徑為如上所述之20.0nm。Figure 3 shows the crystallite diameter of an example of silicon micronanoparticles obtained as a result of an example of one-stage pulverization using X-ray diffraction equipment (Rigaku Co., Ltd., product name "SmartLab") for measurement and analysis A graph of the results of the distribution. In FIG. 3, the horizontal axis represents crystallite diameter (nm), and the vertical axis represents frequency. In addition, the solid line shows the crystallite diameter distribution based on the number distribution, and the dotted line shows the crystallite diameter distribution based on the volume distribution. In the number distribution, the Mode diameter is 0.29nm, the Median diameter (50% crystallite diameter) is 0.75nm, and the average diameter is 1.2nm. In addition, in the volume distribution, the mode diameter is 4.9 nm, the median diameter is 12.5 nm, and the average diameter is 20.0 nm as described above.
圖4為顯示作為藉由X光繞射裝置（XRD）測量分析，作為二階段粉碎之實施例的結果，所得到的矽微小奈米粒子的微晶直徑分佈的結果的圖。在圖4中，横軸表示微晶直徑（nm），縱軸表示頻率。又，實線顯示個數分佈基準的微晶直徑分佈，虛線顯示體積分佈基準的微晶直徑分佈。如圖4所示，在個數分佈中，模式直徑為0.14nm，中位直徑（50%微晶直徑）為0.37nm，平均直徑為0.6nm。又，在體積分佈中，模式直徑為2.6nm，中位直徑為6.7nm，平均直徑為如上所述之10.9nm。藉由該等結果，可以知道二階段粉碎後所得到的矽微小奈米粒子，比起一階段粉碎，可以達成約1/2以下的微小化。藉由使用上述各實施例的珠磨法的粉碎處理，確認得到了微晶直徑分佈在100nm以下之範圍，特別是50nm以下之範圍的矽微小奈米粒子。4 is a graph showing the result of the crystallite diameter distribution of the obtained silicon micro-nanoparticles as a result of the measurement and analysis by an X-ray diffraction device (XRD) as a result of an example of two-stage pulverization. In FIG. 4, the horizontal axis represents crystallite diameter (nm), and the vertical axis represents frequency. In addition, the solid line shows the crystallite diameter distribution based on the number distribution, and the dotted line shows the crystallite diameter distribution based on the volume distribution. As shown in Figure 4, in the number distribution, the mode diameter is 0.14 nm, the median diameter (50% crystallite diameter) is 0.37 nm, and the average diameter is 0.6 nm. In addition, in the volume distribution, the mode diameter is 2.6 nm, the median diameter is 6.7 nm, and the average diameter is 10.9 nm as described above. Based on these results, it can be known that the silicon micronanoparticles obtained after the two-stage pulverization can be reduced by about 1/2 or less than that of the one-stage pulverization. Through the pulverization treatment using the bead milling method of each of the above-mentioned examples, it was confirmed that silicon micronanoparticles with a crystallite diameter distribution in the range of 100 nm or less, especially in the range of 50 nm or less, were obtained.
以下詳細說明使用以一階段粉碎與二階段粉碎所製造的矽微小奈米粒子之含氫溶液或富氫水的生成與其溶解氫濃度的控制。The following is a detailed description of the generation of hydrogen-containing solution or hydrogen-rich water and the control of dissolved hydrogen concentration using silicon micro-nanoparticles produced by one-stage pulverization and two-stage pulverization.
上述以一階段粉碎與二階段粉碎所製造的包含小珠的矽微小奈米粒子可以經由下述工序得到。具體而言，使用安裝在小珠分離容器（AIMEX股份公司製造）上的SUS過濾器（在φ:0.5mm的小珠的情況下，過濾器使用網孔0.35mm，在φ:0.3mm的小珠的情況下使用網孔0.06mm），從其上部注入異丙醇（IPA）溶液，其包含含有小珠的矽微小奈米粒子。其後，藉由進行分級處理、吸引過濾、分離小珠，而得到包含矽微小奈米粒子的IPA溶液。其後，藉由使用減壓蒸發裝置，在40℃將IPA進行蒸發處理，而得到矽微小奈米粒子。The silicon micronanoparticles containing beads produced by the above-mentioned one-stage pulverization and two-stage pulverization can be obtained through the following steps. Specifically, a SUS filter mounted on a bead separation container (manufactured by AIMEX Co., Ltd.) is used (in the case of beads of φ: 0.5 mm, the filter uses a mesh of 0.35 mm, and the size of the filter is 0.35 mm. In the case of beads, a mesh (0.06mm) is used, and an isopropyl alcohol (IPA) solution is injected from the upper part, which contains silicon micro-nanoparticles containing small beads. After that, by performing classification treatment, suction filtration, and separation of beads, an IPA solution containing silicon micro-nanoparticles is obtained. After that, by using a vacuum evaporation device, the IPA was evaporated at 40°C to obtain silicon micro-nanoparticles.
接著，在進行與氟酸溶液接觸或浸漬在氟酸溶液中之處理（以下，也單純稱為「氟酸處理」。）的情況下，追加以下的處理。將得到的矽微小奈米粒子浸漬在5%濃度的氟酸溶液中10分鐘。其後，以100nm的氟樹脂製的膜過濾器在大氣中進行過濾處理，將矽微小奈米粒子收集在膜過濾器上，呈層狀殘存。將此膜過濾器上的矽微小奈米粒子置於氟樹脂製燒杯上，在進行過氟酸處理的情況下，從其上滴加乙醇，以除去氟酸成分。將膜過濾器上的矽微小奈米粒子在空氣中進行30分鐘左右的乾燥處理，而得到進行過氟酸處理的矽微小奈米粒子。Next, in the case of performing the treatment of contacting or immersing in the hydrofluoric acid solution (hereinafter, also simply referred to as "fluoric acid treatment"), the following treatments are added. The obtained silicon micro-nanoparticles were immersed in a 5% hydrofluoric acid solution for 10 minutes. After that, a membrane filter made of 100nm fluororesin was filtered in the atmosphere, and the silicon micro-nanoparticles were collected on the membrane filter and remained in a layered form. The silicon micro-nanoparticles on the membrane filter are placed on a fluororesin beaker, and when the hydrofluoric acid treatment is performed, ethanol is added dropwise to remove the hydrofluoric acid component. The silicon micro-nanoparticles on the membrane filter are dried in the air for about 30 minutes to obtain hydrofluoric acid-treated silicon micro-nanoparticles.
藉由XPS法測量該等矽微小奈米粒子表面的氧化矽膜厚。在未進行氟酸處理的情況下，具有膜厚為1.6nm左右的氧化矽膜。在進行過氟酸處理的情況下，氧化膜被蝕刻除去，成為0.07nm以下，幾乎不具有氧化膜。The thickness of the silicon oxide film on the surface of the silicon micronanoparticles was measured by the XPS method. In the case where the hydrofluoric acid treatment is not performed, it has a silicon oxide film with a thickness of about 1.6 nm. When the hydrofluoric acid treatment is performed, the oxide film is etched and removed, and becomes 0.07 nm or less, and there is almost no oxide film.
將得到的矽微小奈米粒子10mg置入容量30ml的玻璃瓶（硼矽酸玻璃，厚度1mm左右，ASONE公司製造的Laboran螺旋管瓶），其後，投入乙醇1ml，使之分散，添加預定的水溶液約29ml，使全量成為30ml，填滿到玻璃瓶的開口為止，以不讓空氣進入的方式蓋上內蓋，並蓋上蓋子（長1cm），將其完全密封。蓋子為聚丙烯（厚度2mm），內蓋使用聚乙烯與聚丙烯的多層過濾器製造者。藉由上述結構，可以充分減緩生成的氫的穿透或洩漏。Put 10mg of the obtained silicon micro-nanoparticles into a 30ml glass bottle (borosilicate glass, thickness of about 1mm, Laboran screw vial manufactured by ASONE), then add 1ml of ethanol to disperse it, and add the predetermined amount About 29ml of the aqueous solution, make the total volume 30ml, fill it up to the opening of the glass bottle, cover the inner cap so that no air enters, and close the cap (length 1cm) to completely seal it. The cover is made of polypropylene (thickness 2mm), and the inner cover uses a multilayer filter manufacturer of polyethylene and polypropylene. With the above structure, the penetration or leakage of the generated hydrogen can be sufficiently slowed down.
在保持此狀態之下，在室溫下，在密閉的玻璃瓶中從矽微小奈米粒子逐漸生成氫，可以使具有預定濃度的氫溶解在水溶液中，而能夠得到安全的含氫溶液或富氫水。In this state, at room temperature, hydrogen is gradually generated from silicon micro-nanoparticles in a sealed glass bottle. Hydrogen with a predetermined concentration can be dissolved in the aqueous solution, and a safe hydrogen-containing solution or rich solution can be obtained. Hydrogen water.
在水溶液中的溶解氫濃度的反應時間相依性的測量時，使用東亞DKK公司製造的可攜式溶解氫濃度計。首先，圖5中顯示使用未進行氟酸處理之情況下的矽微小奈米粒子的pH値為7的超純水的情況下的測量結果。In the measurement of the reaction time dependence of the dissolved hydrogen concentration in the aqueous solution, a portable dissolved hydrogen concentration meter manufactured by Toa DKK was used. First, Fig. 5 shows the measurement results in the case of using ultrapure water with a pH value of 7 of silicon micro-nanoparticles without fluoric acid treatment.
圖5顯示未粉碎高純度矽粉末、一階段粉碎（平均晶粒直徑20.0nm）、及二階段粉碎（平均晶粒直徑10.9nm）的超純水溶液中的溶解氫濃度的測量値。可以理解由於粒徑（微晶直徑）變小，矽微小奈米粒子的表面積增大，在表面上反應生成的氫增加，溶解氫濃度增加。又，隨著反應時間的增加得到的溶解氫濃度增大，在400分鐘（約7小時）左右的反應下，即使在超純水中也達成了0.4ppm左右的溶解氫濃度。為了得到1ppm以上的溶解氫濃度，只要增加矽微小奈米粒子的量即可。Figure 5 shows the measured values of the dissolved hydrogen concentration in an ultrapure aqueous solution of unpulverized high-purity silicon powder, primary pulverization (average crystal grain diameter 20.0nm), and two-phase pulverization (average crystal grain diameter 10.9nm). It can be understood that as the particle size (crystallite diameter) becomes smaller, the surface area of the silicon micronanoparticles increases, the hydrogen generated by the reaction on the surface increases, and the dissolved hydrogen concentration increases. In addition, the dissolved hydrogen concentration obtained increased with the increase of the reaction time, and a dissolved hydrogen concentration of about 0.4 ppm was reached even in ultrapure water in a reaction of about 400 minutes (about 7 hours). In order to obtain a dissolved hydrogen concentration of 1 ppm or more, it is only necessary to increase the amount of silicon micro-nanoparticles.
又，可見到水溶液中的溶解氫濃度對於水溶液的pH値也具有相依性。具體而言，很明確可見使pH値為8.0時，與超純水相比，水溶液中的溶解氫濃度大量增加。In addition, it can be seen that the dissolved hydrogen concentration in the aqueous solution also has a dependency on the pH value of the aqueous solution. Specifically, it is clearly seen that when the pH value is set to 8.0, the dissolved hydrogen concentration in the aqueous solution is greatly increased compared with ultrapure water.
圖6顯示藉由對進行過一階段粉碎的矽微小奈米粒子（平均微晶直徑20.0nm）施加氟酸處理除去氧化膜的情況下的例子（圖中的三角標記）、與未施加氟酸處理的情況下的例子（圖中的×標記）做比較的結果。此外，兩者的水溶液的pH値均為8。Figure 6 shows an example of the case where the oxide film is removed by hydrofluoric acid treatment on silicon micronanoparticles (average crystallite diameter 20.0nm) that have been pulverized in one step (the triangle mark in the figure), and the case where hydrofluoric acid is not applied The example of the processing case (marked by × in the figure) is the result of comparison. In addition, the pH value of both aqueous solutions is 8.
在使用進行過氟酸處理的矽微小奈米粒子的情況下，在20分鐘左右達成超過1ppm、在100分鐘達成超過1.4ppm的溶解氫濃度。在欲進一步縮短時間的情況下，只要增加矽微小奈米粒子的投入量即可。In the case of using hydrofluoric acid-treated silicon micronanoparticles, a dissolved hydrogen concentration exceeding 1 ppm was achieved in about 20 minutes, and a dissolved hydrogen concentration exceeding 1.4 ppm was achieved in 100 minutes. In the case of further shortening the time, it is only necessary to increase the input amount of silicon micro-nanoparticles.
又，使用日本國之標準飲用可能的自來水（pH値7.1-7.3左右），進行一階段粉碎，未進行氟酸處理的情況下的矽微小奈米粒子（平均微晶直徑20.0nm）混合至自來水中而製造含氫溶液或富氫水。圖7顯示其測量値，也同時顯示使用超純水取代自來水的情況下的測量値。In addition, use Japanese standard drinking water (pH value around 7.1-7.3) for one-stage pulverization, and mix the silicon micro-nanoparticles (average crystallite diameter 20.0nm) without hydrofluoric acid treatment into the tap water. In the production of hydrogen-containing solution or hydrogen-rich water. Figure 7 shows the measured value, and also shows the measured value when ultrapure water is used instead of tap water.
如圖7所示，比起混合在超純水（pH値7.0）中時的溶解氫濃度，顯示顯著的增加，在200分鐘左右達成了1ppm。As shown in Figure 7, compared to the dissolved hydrogen concentration when mixed in ultrapure water (pH 7.0), it showed a significant increase, reaching 1 ppm in about 200 minutes.
此外，將進行過二階段粉碎的矽微小奈米粒子（平均微晶直徑為10.9nm）混合於自來水中，製造含氫溶液或富氫水。雖然未圖示，其結果為，比起使用一階段粉碎的矽微小奈米粒子的情況的溶解氫濃度，進一步增加了1.4-1.6倍左右。In addition, silicon micro-nanoparticles (average crystallite diameter of 10.9nm) that have undergone two-stage pulverization are mixed in tap water to produce a hydrogen-containing solution or hydrogen-rich water. Although not shown in the figure, as a result, the dissolved hydrogen concentration is further increased by about 1.4-1.6 times compared with the case of using one-stage crushed silicon micro-nanoparticles.
可了解能夠使用自來水、未進行氟酸處理、以低成本得到安全的氫濃度1ppm以上的含氫溶液或富氫水。在欲進一步縮短時間的情況下，只要增加矽微小奈米粒子的投入量即可。It is understood that tap water can be used without hydrofluoric acid treatment, and a safe hydrogen-containing solution or hydrogen-rich water with a hydrogen concentration of 1 ppm or more can be obtained at low cost. In the case of further shortening the time, it is only necessary to increase the input amount of silicon micro-nanoparticles.
圖8顯示為了比較施加氟酸處理的情況與未施加氟酸處理的情況，將進行過一階段粉碎的矽微小奈米粒子分散在超純水（pH値7.0）中時的溶解氫濃度的經時變化的測量結果。此外，在進行過氟酸處理的情況下，儘管是相對地較短的20小時，也達成了1ppm溶解氫濃度。在未進行氟酸處理的情況下，經過160小時（1週左右）之後，達成1ppm溶解氫濃度。Figure 8 shows the comparison of the concentration of dissolved hydrogen in the case where the hydrofluoric acid treatment is applied and the case where the hydrofluoric acid treatment is not applied. Time change measurement results. In addition, in the case of hydrofluoric acid treatment, a dissolved hydrogen concentration of 1 ppm was reached despite a relatively short 20 hours. Without the hydrofluoric acid treatment, after 160 hours (about 1 week), a dissolved hydrogen concentration of 1 ppm was reached.
從上述結果可以判斷，在未進行氟酸處理的情況下，由於矽微小奈米粒子的表面存在氧化矽膜，因此矽微小奈米粒子之在超純水中的氫生成反應，其氧化矽膜在超純水中一邊逐漸溶解，一邊極緩慢地發生。其結果為，氫濃度在長時間下，一邊增加一邊持續，如圖8所示。From the above results, it can be judged that in the absence of hydrofluoric acid treatment, there is a silicon oxide film on the surface of the silicon micronanoparticles. Therefore, the hydrogen generation reaction of the silicon micronanoparticles in ultrapure water causes the silicon oxide film While gradually dissolving in ultrapure water, it occurs extremely slowly. As a result, the hydrogen concentration continued to increase while increasing over a long period of time, as shown in FIG. 8.
[實施例2] 基於添附的圖式詳細說明本發明之其他的實施形態（實施例2）。[Embodiment 2] Another embodiment of the present invention (Embodiment 2) will be described in detail based on the attached drawings.
矽微小奈米粒子係如下製造，即，使用珠磨裝置（AIMEX股份公司製:RMB型批式Ready研磨機），使高純度矽（Si）粉末（例如，高純度化學研究所公司製造，粒度分佈＜φ5μm，純度99.9%，i型矽））60g分散在99.5wt%的乙醇250ml中，加入φ;0.5μm的氧化鋯製小珠（容量300ml），以旋轉數2500rpm進行粉碎（一階段粉碎）4小時。Silicon micro-nanoparticles are manufactured as follows, that is, using a bead milling device (manufactured by AIMEX Co., Ltd.: RMB type batch-ready mill) to make high-purity silicon (Si) powder (for example, manufactured by High-Purity Chemical Research Institute Co., Ltd., particle size Distribution <φ5μm, purity 99.9%, i-type silicon)) 60g dispersed in 99.5wt% ethanol 250ml, add φ;0.5μm zirconia beads (capacity 300ml), pulverize at 2500rpm (one-stage pulverization) )4 hours.
藉由本實施例中之珠磨機的一階段粉碎工序所得到的體積分佈及矽微小奈米粒子的結晶結構，可以判斷係與實施例1大略相同的結果。According to the volume distribution obtained by the one-stage pulverization process of the bead mill in this embodiment and the crystal structure of the silicon micro-nanoparticles, it can be judged that the result is roughly the same as that of the first embodiment.
以下詳細說明以乙醇中的一階段粉碎製造、使用後述之過氧化氫溶液處理後的矽微小奈米粒子的含氫溶液或富氫水的生成與其溶解氫濃度及氫生成量的控制。The following describes in detail the production of a hydrogen-containing solution or hydrogen-rich water of silicon micronanoparticles produced by one-stage pulverization in ethanol and treated with a hydrogen peroxide solution described later, and the control of the dissolved hydrogen concentration and the amount of hydrogen produced.
上述包含藉由進行乙醇中的一階段粉碎所得到的小珠的矽微小奈米粒子可以經由以下工序得到。具體而言，使用安裝在小珠分離容器（AIMEX股份公司製）上的SUS過濾器（在φ:0.5mm的小珠的情況下過濾器的網孔為0.35mm，在φ:0.3mm的小珠的情況下使用網孔0.06mm），從其上部注入乙醇溶液，其包含含有小珠的矽微小奈米粒子。其後，藉由分級處理、吸引過濾、分離小珠，得到包含矽微小奈米粒子的乙醇溶液。其後，藉由使用減壓蒸發裝置，在30℃-35℃下對乙醇進行蒸發處理，得到矽微小奈米粒子及/或其凝聚體（以下，作為總稱也稱為「矽微小奈米粒子」）。The above-mentioned silicon micronanoparticles containing beads obtained by performing one-stage pulverization in ethanol can be obtained through the following steps. Specifically, a SUS filter mounted on a bead separation container (manufactured by AIMEX Co., Ltd.) is used (in the case of beads of φ: 0.5 mm, the mesh of the filter is 0.35 mm, and the mesh size of the filter is 0.35 mm in the case of beads of φ: 0.3 mm. In the case of beads, a mesh (0.06mm) is used, and an ethanol solution is injected from the top of the beads, which contains silicon micro-nanoparticles containing small beads. After that, by classification treatment, suction filtration, and separation of beads, an ethanol solution containing silicon micro-nanoparticles is obtained. After that, by using a reduced-pressure evaporation device to evaporate ethanol at 30°C to 35°C, silicon micro-nanoparticles and/or aggregates thereof are obtained (hereinafter, also referred to as "silicon micro-nanoparticles" as a general term). ").
作為過氧化氫溶液處理，將得到的矽微小奈米粒子投入內含過氧化氫溶液（例如，3.5wt%，100ml）的耐熱性玻璃中，進行30分鐘加熱處理（溫度約75℃）。As a hydrogen peroxide solution treatment, the obtained silicon micronanoparticles are put into a heat-resistant glass containing a hydrogen peroxide solution (for example, 3.5 wt%, 100 ml), and heat treatment is performed (at a temperature of about 75°C) for 30 minutes.
把過氧化氫溶液處理後的矽微小奈米粒子移到離心管中，藉由離心處理，進行固液分離，將液體丟棄，重新投入乙醇（例如，3.5%或99.5%，100ml）。其後，在乙醇中攪拌矽微小奈米粒子，進行同樣的離心，進行與上述相同的處理。其後，同樣地，加入與上述同量的乙醇，進行與上述同樣的離心處理，而得到矽微小奈米粒子。The silicon micro-nanoparticles treated with the hydrogen peroxide solution are transferred to a centrifuge tube, the solid-liquid separation is performed by centrifugation, the liquid is discarded, and ethanol is refilled (for example, 3.5% or 99.5%, 100ml). Thereafter, the silicon micronanoparticles were stirred in ethanol, and the same centrifugation was performed, and the same treatment as above was performed. Thereafter, in the same manner, the same amount of ethanol as described above was added, and the same centrifugal treatment as described above was performed to obtain silicon micro-nanoparticles.
其後，進行自然乾燥1天左右（長時間）。在經過1天左右後的狀態下，可以認為乙醇及過氧化氫溶液已大略完全被除去。After that, natural drying is performed for about 1 day (long time). In the state after about 1 day, it can be considered that the ethanol and hydrogen peroxide solution have been almost completely removed.
又，作為上述例子的其他例子，進行過氧化氫溶液60分鐘加熱處理（溫度約75℃）及同樣的離心處理，而得到矽微小粒子。In addition, as another example of the above example, a hydrogen peroxide solution was heated for 60 minutes (at a temperature of about 75°C) and the same centrifugation treatment was performed to obtain silicon fine particles.
如上所述，藉由將與過氧化氫溶液混合的矽微小奈米粒子，使用已知的離心處理裝置，藉由固液分離處理除去過氧化氫溶液，可以得到藉由過氧化氫溶液進行了表面處理的矽微小奈米粒子。此外，藉由以過氧化氫溶液進行表面處理，能夠除去存在矽微小奈米粒子表面上的烷基（例如，甲基）。其結果為，該矽微小奈米粒子及其凝聚體可以形成為，其整體可以保持表面的親水性，並同時也具有可以與可包含水含有液的媒介直接接觸的表面的狀態。藉由施加此種特殊的表面處理，能夠以更高準確性促進氫的生成。As described above, by mixing silicon micronanoparticles mixed with hydrogen peroxide solution and using a known centrifugal treatment device to remove the hydrogen peroxide solution by solid-liquid separation treatment, it is possible to obtain Surface-treated silicon micro-nanoparticles. In addition, by performing surface treatment with hydrogen peroxide solution, it is possible to remove alkyl groups (for example, methyl groups) present on the surface of silicon micro-nanoparticles. As a result, the silicon micro-nanoparticles and their aggregates can be formed so that they can maintain the hydrophilicity of the surface as a whole, and at the same time, have a surface that can directly contact a medium that may contain a water-containing liquid. By applying such a special surface treatment, the generation of hydrogen can be promoted with higher accuracy.
將藉由上述各工序得到的矽微小奈米粒子11mg（過氧化氫溶液處理（30分鐘處理））置入容量115ml的玻璃瓶（硼矽酸玻璃厚度1mm左右，ASONE公司製造Laboran螺旋管瓶）中，使其分散，使全量成為115ml的方式添加預定的水溶液（純水）約115ml與碳酸氫鈉（符合日本藥典者，投入約20g，使其成為1.88wt%，得到pH約8.3）。其後，填滿到玻璃瓶的開口為止，以不讓空氣進入的方式蓋上內蓋，並蓋上蓋子（長1cm），將其完全密封。蓋子的材質為聚丙烯（厚度2mm），內蓋使用聚乙烯與聚丙烯的多層過濾器製造者。藉由上述結構，可以充分減緩生成的氫的穿透或洩漏。矽微小奈米粒子直接以該狀態均勻地混合在水溶液的整體之中。這可以認為是由於藉由過氧化氫溶液處理，矽微小奈米粒子有效地成為親水性的緣故。換言之，可以認為是藉由過氧化氫溶液處理，在適當保持矽微小粒子表面的親水性的同時，可以實現具有可以與該水溶液直接接觸的充分的表面積的狀態。Put 11 mg of silicon micro-nanoparticles (treated with hydrogen peroxide solution (30 minutes treatment)) obtained through the above steps into a glass bottle with a capacity of 115 ml (the thickness of borosilicate glass is about 1 mm, and the Laboran spiral tube bottle manufactured by ASONE) In the medium, it is dispersed and the total amount becomes 115ml. Approximately 115ml of a predetermined aqueous solution (pure water) and sodium bicarbonate (approximately 20g is added to the Japanese Pharmacopoeia to make it 1.88wt% to obtain a pH of approximately 8.3). After that, fill up to the opening of the glass bottle, close the inner cap so that no air can enter, and close the cap (length 1cm) to completely seal it. The material of the cover is polypropylene (thickness 2mm), and the inner cover uses a multilayer filter manufacturer of polyethylene and polypropylene. With the above structure, the penetration or leakage of the generated hydrogen can be sufficiently slowed down. The silicon micro-nanoparticles are directly mixed in this state evenly in the whole aqueous solution. This can be thought to be due to the fact that the silicon micronanoparticles effectively become hydrophilic by the hydrogen peroxide solution treatment. In other words, it can be considered that the hydrogen peroxide solution treatment can appropriately maintain the hydrophilicity of the surface of the silicon fine particles while achieving a state having a sufficient surface area that can be directly contacted with the aqueous solution.
此外，關於過氧化氫溶液處理（60分鐘處理），使用矽微小奈米粒子5mg，進行氫生成的實驗。In addition, regarding the hydrogen peroxide solution treatment (60 minutes treatment), 5 mg of silicon micro-nanoparticles were used to conduct hydrogen generation experiments.
在保持完全密封的狀態下，在室溫下，在密閉的玻璃瓶中從矽微小奈米粒子逐漸生成氫，可以使具有預定的濃度的氫溶解在水溶液中。因此，在實施例2中，由於沒有像實施例1一樣使用IPA或氟酸，因此值得特別說明的是，可以藉由對活體或活體內更安全安心的藥液與工程處理而得到矽微小奈米粒子及含氫溶液或富氫水。In a completely sealed state, hydrogen is gradually generated from silicon micro-nanoparticles in a sealed glass bottle at room temperature, and hydrogen with a predetermined concentration can be dissolved in an aqueous solution. Therefore, in Example 2, since IPA or hydrofluoric acid was not used as in Example 1, it is worth noting that it is possible to obtain silicon micronaphthalenes through safer and more reliable medical solutions and engineering treatments in vivo or in vivo. Rice particles and hydrogen-containing solution or hydrogen-rich water.
水溶液中的溶解氫濃度的反應時間相依性的測量係使用東亞DKK公司製造的可攜式溶解氫濃度計。在圖9（a）中，顯示使用以下三種矽微小奈米粒子時的溶解氫濃度的測量結果：未進行過氧化氫溶液處理的情況下的矽微小奈米粒子、用過氧化氫溶液處理30分鐘的矽微小奈米粒子、或使用過氧化氫溶液處理60分鐘的矽微小奈米粒子。又，圖9（b）表示針對上述各條件，顯示換算成每1g矽（Si）的氫生成量。圖9（a）的縱軸表示溶解氫濃度，横軸表示反應時間（h:小時）。又，圖9（b）的縱軸表示氫生成量，横軸表示反應時間（h:小時）。The reaction time dependence of the dissolved hydrogen concentration in the aqueous solution was measured using a portable dissolved hydrogen concentration meter manufactured by Dong-A DKK Corporation. Figure 9(a) shows the measurement results of the dissolved hydrogen concentration when using the following three types of silicon micro-nanoparticles: silicon micro-nanoparticles without hydrogen peroxide solution treatment, 30 Minutes of silicon nano-particles or hydrogen peroxide solution for 60 minutes of silicon micro-nanoparticles. In addition, FIG. 9(b) shows the amount of hydrogen generated per 1g of silicon (Si) for each of the above conditions. The vertical axis of Fig. 9(a) represents the dissolved hydrogen concentration, and the horizontal axis represents the reaction time (h: hour). In addition, the vertical axis of FIG. 9(b) represents the amount of hydrogen generation, and the horizontal axis represents the reaction time (h: hour).
如圖9所示，藉由過氧化氫溶液處理，氫生成快速增大。此係由於矽微小奈米粒子成為親水性，並均勻分散於水溶液中之故。在採用「過氧化氫溶液處理（30分鐘處理）」的條件時，得到值得說明的濃度為在2小時400ppb、在4小時接近1000ppb。又，在24小時達到了2000ppb。As shown in Figure 9, the hydrogen peroxide solution treatment rapidly increased hydrogen production. This is due to the fact that silicon micro-nanoparticles become hydrophilic and are uniformly dispersed in the aqueous solution. When the conditions of "hydrogen peroxide solution treatment (30 minutes treatment)" are used, the descriptive concentration is 400 ppb in 2 hours and close to 1000 ppb in 4 hours. In addition, it reached 2000ppb in 24 hours.
另一方面，在採用「過氧化氫溶液處理（60分鐘處理）」的條件的情況下，氫生成量比起「過氧化氫溶液處理（30分鐘處理）」的條件時低。此係由於採用「過氧化氫溶液處理（60分鐘處理）」的條件，則矽微小奈米粒子的表面氧化膜比「過氧化氫溶液處理（30分鐘處理）」的條件時的膜厚更厚，因此氫生成量受到抑制。此外，雖然在此未圖示，然而以「過氧化氫溶液處理（15分鐘處理）」的條件進行了與上述同樣的實驗，得到的實驗結果與「過氧化氫溶液處理（30分鐘處理）」的條件大略相同。在1-2分鐘處理時，與無處理時為相同程度，沒有得到有效的氫生成。On the other hand, when the conditions of "hydrogen peroxide solution treatment (60 minutes treatment)" are used, the amount of hydrogen generation is lower than that under the conditions of "hydrogen peroxide solution treatment (30 minutes treatment)". This is due to the "hydrogen peroxide solution treatment (60 minutes treatment)" conditions, the surface oxide film of the silicon micronanoparticles is thicker than the "hydrogen peroxide solution treatment (30 minutes treatment)" conditions , So the amount of hydrogen production is suppressed. In addition, although not shown here, the same experiment as above was performed under the conditions of "hydrogen peroxide solution treatment (15 minutes treatment)", and the experimental results obtained are the same as "hydrogen peroxide solution treatment (30 minutes treatment)" The conditions are roughly the same. When treated for 1-2 minutes, it was the same level as when there was no treatment, and effective hydrogen generation was not obtained.
因此，過氧化氫溶液處理的時間以5-30分鐘為適當。混合碳酸氫鈉，可以相當於一般活體的小腸的pH狀態，在體內產生有效的氫生成。圖9（b）顯示換算成每1gSi的氫生成量。縱軸表示每1gSi的氫生成量（ml），横軸表示反應時間（h:小時）。如圖9（b）所示，在過氧化氫溶液處理（30分鐘處理）的條件下，可以在2小時以上持續得到極有效的氫生成量（40ml）。Therefore, the appropriate time for the hydrogen peroxide solution treatment is 5-30 minutes. Mixing sodium bicarbonate can be equivalent to the pH state of the small intestine of a general living body, producing effective hydrogen production in the body. Figure 9(b) shows the amount of hydrogen generated per 1gSi. The vertical axis represents the amount of hydrogen produced per 1 g of Si (ml), and the horizontal axis represents the reaction time (h: hour). As shown in Figure 9(b), under the conditions of hydrogen peroxide solution treatment (30 minutes treatment), extremely effective hydrogen production (40ml) can be continuously obtained for more than 2 hours.
從上述實驗結果來看，不使用IPA或氟酸，可以製造即使使用在活體，也更安全且安心的矽微小奈米粒子，因此可以安全地在活體內使氫生成。進一步而言，使用此矽微小奈米粒子，加入已知的添加劑或食品中，可以製造活體用氫生成材料。According to the above experimental results, without using IPA or hydrofluoric acid, it is possible to produce silicon micro-nanoparticles that are safer and more secure even when used in a living body, so hydrogen can be generated safely in a living body. Furthermore, the use of these silicon micro-nanoparticles can be added to known additives or foods to produce hydrogen-generating materials for living organisms.
為了在反應時間數小時以內得到1ppm以上的溶解氫濃度，只要增加矽微小奈米粒子的量即可。In order to obtain a dissolved hydrogen concentration of 1 ppm or more within a few hours of reaction time, it is only necessary to increase the amount of silicon micro-nanoparticles.
然而，作為矽微小粒子，除了高純度矽（Si）粉末以外，利用太陽能電池級的矽基板的切割加工時所生成的矽切粉或半導體級的研磨屑，也可以生成含氫溶液或富氫水。又，不只是i型，也可以使用n型、p型。However, as fine silicon particles, in addition to high-purity silicon (Si) powder, silicon chips or semiconductor-grade grinding debris generated during the cutting process of solar cell-grade silicon substrates can also be used to generate hydrogen-containing solutions or hydrogen-rich water. In addition, not only the i-type, but also n-type and p-type can be used.
產業上之利用可能性Industrial possibilities
本發明係可以製造具有活體安全性的矽微小奈米粒子，並可以將其有效利用而發展成具有優異的安全性、實用性及經濟性的含氫溶液或富氫水與其製造技術者，特別是，可以利用至含有健康、醫療用矽微小奈米粒子的氫生成材料（劑）、洗淨水、或健康飲用水等健康、醫療食品、產品領域。The present invention can produce silicon micronanoparticles with biosafety, and can be effectively used to develop hydrogen-containing solutions or hydrogen-rich water with excellent safety, practicability, and economy, and its manufacturing technology, especially Yes, it can be used in the fields of health and medical food and products such as hydrogen generating materials (agents) containing silicon micro-nanoparticles for health and medical purposes, clean water, or healthy drinking water.
無no
圖1係顯示實施例中之一階段粉碎後的矽微小奈米粒子的結晶結構例的斷面TEM（穿透式電子顯微鏡）照片圖。 圖2係針對個別的矽微小奈米粒子擴大後的TEM照片。 圖3係在實施例的一階段粉碎得到的矽微小奈米粒子的藉由X光繞射裝置（XRD）的微晶直徑分佈圖。 圖4係在實施例的二階段粉碎得到的矽微小奈米粒子的藉由XRD的微晶直徑分佈圖。 圖5係在實施例得到的含氫溶液或富氫水中的溶解氫濃度特性圖。 圖6係在實施例得到的含氫溶液或富氫水中的溶解氫濃度特性圖。 圖7係在實施例得到的含氫溶液或富氫水中的溶解氫濃度特性圖。 圖8係在實施例得到的含氫溶液或富氫水中的溶解氫濃度特性圖。 圖9（a）係在其他的實施例得到的含氫溶液或富氫水中的溶解氫濃度特性圖；圖9（b）係在其他的實施例得到的含氫溶液或富氫水中的換算成每1g矽（Si）的氫生成量特性圖。Fig. 1 is a cross-sectional TEM (transmission electron microscope) photograph showing an example of the crystal structure of silicon micro-nanoparticles pulverized in one stage of the embodiment. Figure 2 is an enlarged TEM image of individual silicon micro-nanoparticles. Figure 3 is a diagram of the crystallite diameter distribution of the silicon micronanoparticles obtained by pulverization in one stage of the embodiment by X-ray diffraction device (XRD). Figure 4 is the XRD crystallite diameter distribution diagram of the silicon micronanoparticles obtained in the two-stage pulverization of the embodiment. Fig. 5 is a characteristic diagram of the dissolved hydrogen concentration in the hydrogen-containing solution or hydrogen-rich water obtained in the embodiment. Figure 6 is a characteristic diagram of the dissolved hydrogen concentration in the hydrogen-containing solution or hydrogen-rich water obtained in the embodiment. Figure 7 is a characteristic diagram of the dissolved hydrogen concentration in the hydrogen-containing solution or hydrogen-rich water obtained in the embodiment. Figure 8 is a graph showing the concentration characteristics of dissolved hydrogen in the hydrogen-containing solution or hydrogen-rich water obtained in the examples. Fig. 9(a) is a characteristic diagram of dissolved hydrogen concentration in a hydrogen-containing solution or hydrogen-rich water obtained in other embodiments; Fig. 9(b) is a conversion of hydrogen-containing solutions or hydrogen-rich water obtained in other embodiments Characteristic graph of the amount of hydrogen produced per 1g of silicon (Si).
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| JP2016155118A (en) * | 2015-02-24 | 2016-09-01 | 小林 光 | Hydrogen water, and method and apparatus for producing the same |
| JP2017104848A (en) * | 2015-12-04 | 2017-06-15 | 小林 光 | Silicon nanoparticles and/or aggregate thereof, hydrogen generating material for organism and production method for the same, and hydrogen water and production method and production apparatus for the same |
| CN108601798A (en) | 2016-01-29 | 2018-09-28 | 小林光 | Solid pharmaceutical preparation, the preparation method of solid pharmaceutical preparation and liberation of hydrogen method |
| CN110191860A (en) | 2016-08-23 | 2019-08-30 | 小林光 | Composite and its manufacturing method and method of supplying hydrogen |
| CN110191699A (en) * | 2016-08-23 | 2019-08-30 | 小林光 | Hydrogen supplying material and its manufacturing method and method of supplying hydrogen |
| TWI670236B (en) * | 2017-06-16 | 2019-09-01 | 友達晶材股份有限公司 | Filter material |
| CN109126268B (en) * | 2017-06-16 | 2021-07-02 | 友达晶材股份有限公司 | Biological water composition, aggregate thereof, filter material, filter element thereof and water purification system thereof |
| WO2019021769A1 (en) | 2017-07-27 | 2019-01-31 | 国立大学法人大阪大学 | Drug and production method therefor |
| US20190126178A1 (en) * | 2017-10-30 | 2019-05-02 | Auo Crystal Corporation | Filter and Method of Preparing the Same |
| AU2019263820A1 (en) * | 2018-04-29 | 2020-11-26 | Bosquet Silicon Corp. | Composite composition |
| JP7333941B2 (en) * | 2018-06-07 | 2023-08-28 | 国立大学法人大阪大学 | Preventive or therapeutic agent for diseases caused by oxidative stress |
| CN117860776A (en) | 2018-06-07 | 2024-04-12 | 国立大学法人大阪大学 | Preventive or therapeutic agent for oxidative stress-induced diseases |
| JP7345824B2 (en) * | 2018-07-02 | 2023-09-19 | 国立大学法人大阪大学 | Agents for preventing or treating depression or depressive state |
| JP7461003B2 (en) | 2018-11-13 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agents for Parkinson's disease |
| EP3666730A3 (en) * | 2018-12-14 | 2020-08-19 | AUO Crystal Corporation | Filter, filter assembly, filter device and water purification system |
| EP3915637A4 (en) * | 2019-01-24 | 2022-03-16 | Osaka University | Medical agent and method for manufacturing same |
| JP7461005B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for autism spectrum disorder |
| JP7461006B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for arthritis |
| JP7461011B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for hearing loss |
| JP7461007B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agents for visceral discomfort |
| JP7461008B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for disorders or symptoms after spinal cord injury |
| JP7461009B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for diabetes |
| JP7461004B2 (en) | 2019-01-24 | 2024-04-03 | 国立大学法人大阪大学 | Preventive or therapeutic agent for memory disorders |
| WO2021199644A1 (en) | 2020-04-02 | 2021-10-07 | 株式会社ボスケシリコン | Composite material |
| WO2021199850A1 (en) | 2020-04-02 | 2021-10-07 | 株式会社ボスケシリコン | Oxidative stress inhibitor and antioxidant agent |
| CN113716522A (en) * | 2020-05-25 | 2021-11-30 | 硅力能股份有限公司 | Composite material for hydrogen production |
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| GB0515353D0 (en) * | 2005-07-27 | 2005-08-31 | Psimedica Ltd | Food |
| JP2008019115A (en) * | 2006-07-11 | 2008-01-31 | Catalysts & Chem Ind Co Ltd | Method for producing silicon fine particle |
| JP2010265158A (en) * | 2009-05-18 | 2010-11-25 | Mitsubishi Electric Corp | Method for producing silicon fine particle |
| JP2011026211A (en) * | 2009-07-21 | 2011-02-10 | Niigata Univ | Method for producing microcapsule containing hydrogen-generating powder |
| GB0919830D0 (en) * | 2009-11-12 | 2009-12-30 | Isis Innovation | Preparation of silicon for fast generation of hydrogen through reaction with water |
| JP2011218340A (en) * | 2010-04-06 | 2011-11-04 | Norihiko Kabayama | Method for production of electronic water |
| JP5695842B2 (en) * | 2010-06-02 | 2015-04-08 | シャープ株式会社 | Method for producing lithium-containing composite oxide |
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| JP2016155118A (en) * | 2015-02-24 | 2016-09-01 | 小林 光 | Hydrogen water, and method and apparatus for producing the same |
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| TW201836990A (en) | 2018-10-16 |
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| TWI783650B (en) | 2022-11-11 |
| WO2018037752A1 (en) | 2018-03-01 |
| JPWO2018037752A1 (en) | 2019-08-08 |
| JP2016155118A (en) | 2016-09-01 |
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