TWI483797B - A composite of size-controllable metal nanoparticles and its preparation method - Google Patents
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本發明係關於一種金屬粒子與脫層的矽酸鹽黏土之複合材料之製造方法，尤指一種可控制金屬粒子體積的奈米複合材料之製造方法。The invention relates to a method for manufacturing a composite material of metal particles and delaminated silicate clay, in particular to a method for manufacturing a nano composite material capable of controlling the volume of metal particles.
奈米銀粒子具有公認的抗菌效果，可殺死600多種細菌，且為重要的奈米材料之一，其應用面廣泛包含了生物、醫藥，生醫材料、化學、化工、奈米複合材料等。但是在製備的過程中，因為奈米尺寸的效應以及銀粒子本身的凡得瓦爾力(van der Waals force)的親合性，導致分散困難且易聚集。因此控制奈米銀粒子的大小、穩定性、分散性為研究之重要標的。Nano silver particles have a recognized antibacterial effect, can kill more than 600 kinds of bacteria, and are one of the important nano materials. Their application covers bio, medicine, biomedical materials, chemistry, chemicals, nanocomposites, etc. . However, during the preparation process, the dispersion is difficult and easy to aggregate due to the effect of the nanometer size and the affinity of the van der Waals force of the silver particles themselves. Therefore, controlling the size, stability and dispersibility of nano-silver particles is an important subject of research.
製造奈米銀粒子的方法主要分為物理及化學兩種製造方法。其中，物理方法可直接得到奈米銀的粉體，但是需要特殊的設備才能製備，例如以高能量雷射將巨觀態(bulk phase)固態物質裂解成奈米尺度大小的粒子，或將金屬固態物質氣化成氣態金屬蒸氣，再以冷凝聚集成金屬奈米粒子。以上兩種物理製造方法不僅操作複雜，所需設備昂貴。其次，在操作或製造過程中，濃度必須在ppm的規模下才可進行，若提高銀離子濃度，則在還原時易造成銀粒子聚集，因此操作範圍有限。The method for producing nano silver particles is mainly divided into physical and chemical manufacturing methods. Among them, the physical method can directly obtain the powder of nano silver, but requires special equipment to prepare, for example, high-energy laser to crack the bulk phase solid matter into nanometer-sized particles, or metal The solid matter is vaporized into a gaseous metal vapor, which is then condensed and aggregated into metal nanoparticles. The above two physical manufacturing methods are not only complicated in operation but also expensive in equipment required. Secondly, in the operation or manufacturing process, the concentration must be carried out at a scale of ppm. If the concentration of silver ions is increased, silver particles are easily aggregated during reduction, and thus the operation range is limited.
化學還原法是在溶液相中進行氧化還原反應，將銀離 子還原成銀原子。由於還原後的銀粒子容易聚集，故於反應過程中，多會添加穩定劑以吸附在生成的粒子表面，穩定奈米粒子，避免其互相聚集。穩定劑的作用方式包括：The chemical reduction method is to carry out a redox reaction in a solution phase, leaving the silver away. The child is reduced to a silver atom. Since the silver particles after the reduction tend to aggregate, during the reaction, a stabilizer is added to adsorb on the surface of the generated particles, and the nanoparticles are stabilized to avoid aggregation with each other. The mode of action of the stabilizer includes:
(1)藉由靜電排斥力，使粒子表面吸附電荷，形成電雙層，粒子表面帶有相同電荷，則當兩個粒子相互接近，庫侖排斥力會增加，防止粒子凝聚。然而，若表面吸附的陰離子被中性吸附物取代，則表面電荷將減少，凡得瓦爾力將使粒子凝集。另外在高濃度粒子下或溶液離子強度增加時，由於介電強度的增強，電雙層被壓縮，而不利粒子的穩定。(1) By electrostatic repulsion, the surface of the particle is adsorbed to form an electric double layer, and the surface of the particle carries the same charge. When the two particles are close to each other, the Coulomb repulsive force increases to prevent the particles from agglomerating. However, if the anion adsorbed on the surface is replaced by a neutral adsorbate, the surface charge will decrease and the van der Waals force will agglomerate the particles. In addition, under high concentration particles or when the solution ionic strength increases, the electric double layer is compressed due to the enhancement of the dielectric strength, which is disadvantageous for the stability of the particles.
(2)藉由立體阻礙，粒子表面若有吸附穩定劑，藉由有機分子在金屬粒子表面形成保護層，而阻礙粒子的凝聚，此稱為立體穩定。常用的穩定劑種類包括：水溶性高分子類(如PVP、PVA、polymethylvinylether、PAA等)、樹枝狀高分子(dendrimer)、檸檬酸鈉、界面活性劑、配位基或螫合劑等。(2) If there is an adsorption stabilizer on the surface of the particle by the steric hindrance, the organic molecule forms a protective layer on the surface of the metal particle to hinder the aggregation of the particles, which is called steric stabilization. Commonly used stabilizers include: water-soluble polymers (such as PVP, PVA, polymethylvinylether, PAA, etc.), dendrimers, sodium citrate, surfactants, ligands or chelating agents.
傳統使用的穩定劑多為有機高分子類，並利用不同種類的高分子或高分子添加的比例，以製備出不同粒徑大小的高分子與奈米銀的複合材料。然而，該高分子與奈米銀的複合材料受熱易聚集，造成奈米銀粒子變大，而使其應用性受到限制。Most of the stabilizers used in the past are organic polymers, and the ratios of different types of polymers or polymers are used to prepare composites of polymers of different particle sizes and nano-silver. However, the composite material of the polymer and the nano silver is easily aggregated by heat, causing the nano silver particles to become large, and the applicability thereof is limited.
有鑑於此，本案發明人利用無機脫層之片狀黏土作為金屬粒子的分散劑或穩定劑，再藉由化學還原法製備「奈 米金屬粒子與脫層之片狀黏土的複合物」。此脫層之片狀黏土為發明人自行開發之奈米矽片(Nano silicate platelet or NSP)，詳細製備方法可參見中華民國公告第I280261、I284138、I270529、577904及593480等號發明專利。請參閱圖1所示，鈉離子型蒙脫土1藉由高分子2進入層間，將層間撐開達脫層後，再經過一系列萃取以得到該奈米矽片3。將該奈米矽片具有高片徑比(平均為100×100×1 nm3 )、高表面積(700~800 m2 /g)以及強電荷性(ca.20,000離子/片)等特性，平均為4×1016 片/g。基於上述奈米矽片之特性，使奈米矽片能穩定分散銀粒子，並使銀粒子達到奈米級之分散。In view of this, the inventors of the present invention used the inorganic delaminated sheet clay as a dispersant or stabilizer for the metal particles, and then prepared a "composite of the nano metal particles and the delaminated sheet clay" by a chemical reduction method. The delaminated sheet clay is a nano silicate platelet or NSP developed by the inventors. For detailed preparation methods, refer to the invention patents of the Republic of China Announcement Nos. I280261, I284138, I270529, 577904 and 593480. Referring to FIG. 1, the sodium ion type montmorillonite 1 enters the interlayer by the polymer 2, and the interlayer is stretched to the delamination, and then subjected to a series of extraction to obtain the nanosheet 3. The nanosheet has a high aspect ratio (average of 100×100×1 nm 3 ), a high surface area (700-800 m 2 /g), and a strong charge (ca. 20,000 ion/sheet). It is 4 × 10 16 pieces / g. Based on the characteristics of the above-mentioned nano bismuth tablets, the nano sized tablets can stably disperse the silver particles and cause the silver particles to reach the nanometer-level dispersion.
依上述方法所製備出的奈米金屬粒子與脫層之片狀黏土的複合物為無機複合材料，有別於傳統利用有機高分子以還原穩定銀粒子之有機-無機複合材料，且本案發明人有鑑於利用高分子還原成的奈米銀粒子存在著分散困難且易聚集，無法有效的控制奈米銀粒子粒徑大小及提高奈米銀粒子對熱處理的穩定性，更致力於奈米金屬粒子與脫層之片狀黏土複合物的更進一步研究。The composite of the nano metal particles prepared by the above method and the delaminated flaky clay is an inorganic composite material, which is different from the organic-inorganic composite material which uses the organic polymer to reduce and stabilize the silver particles, and the inventor of the present invention In view of the fact that the nano silver particles reduced by the polymer are difficult to disperse and are easy to aggregate, the particle size of the nano silver particles can not be effectively controlled, and the stability of the nano silver particles to heat treatment is improved, and the nano metal particles are further devoted. Further research with delaminated flaky clay complexes.
本發明之主要目的在於提供一種可控制金屬粒子體積的奈米複合材料之製造方法，係可以有效地被控制製成之奈米複合材料的金屬粒子體積者。SUMMARY OF THE INVENTION A primary object of the present invention is to provide a method for producing a nanocomposite material capable of controlling the volume of a metal particle, which is capable of effectively controlling the volume of the metal particle of the nano composite material produced.
本發明之另一目的在於提供一種可控制金屬粒子體 積的奈米複合材料之製造方法，係可使所製造之複合材料中的金屬粒子對熱處理具有高穩定性，而於成膜後再回溶於溶液中時不會產生聚集者。Another object of the present invention is to provide a controllable metal particle body The method for manufacturing the nano composite material is such that the metal particles in the composite material produced have high stability to heat treatment, and do not cause aggregation when dissolved in the solution after film formation.
用以達成上述目的，本發明所提供之一種可控制金屬粒子體積的奈米複合材料之製造方法，主要包含有：A.調製一脫層的矽酸鹽黏土的溶液與一金屬離子溶液；B.將該含脫層的矽酸鹽黏土之溶液與該含金屬離子之溶液混和，以將該金屬離子還原成奈米金屬粒子並分別附著在該等脫層的矽酸鹽黏土上；其中，在步驟A.中，調整該等矽酸鹽黏土和該等金屬離子的重量比，以控制步驟B.中所還原之金屬粒子的體積，且該等矽酸鹽黏土和該等金屬離子的重量比之比值愈大者，該步驟B.中所還原之金屬粒子的體積愈小。The method for manufacturing a nano composite material capable of controlling the volume of a metal particle provided by the present invention mainly comprises: A. preparing a solution of a delaminated citrate clay and a metal ion solution; Mixing the solution of the delaminated citrate clay with the metal ion-containing solution to reduce the metal ions to nano metal particles and attaching to the delaminated tellurite clay, respectively; In step A., adjusting the weight ratio of the citrate clay to the metal ions to control the volume of the metal particles reduced in step B., and the weight of the silicate clay and the metal ions The larger the ratio, the smaller the volume of the metal particles reduced in the step B.
上述之金屬粒子可以選自銀、銅、鐵或金等材料之一，較佳材料為銀。The metal particles described above may be selected from one of materials such as silver, copper, iron or gold, and the preferred material is silver.
上述之脫層的矽酸鹽黏土可以選自皂土、鋰皂土、蒙脫土、人工合成雲母、高嶺土、滑石、凹凸棒土、蛭石或層狀雙氫氧化物中之至少一者經脫層後的片狀黏土，較佳選擇為自蒙脫土脫層的奈米矽片。The delaminated citrate clay may be selected from at least one of bentonite, lithium bentonite, montmorillonite, synthetic mica, kaolin, talc, attapulgite, vermiculite or layered double hydroxide. The delaminated flaky clay is preferably selected from the montmorillonite delamination.
上述之金屬離子溶液可以選自該金屬離子之硝酸鹽溶液、氯化鹽溶液或溴化鹽溶液之一，例如該金屬離子為銀離子，則該溶液選自硝酸銀溶液、氯化銀溶液或溴化銀溶液之一。The metal ion solution may be selected from one of a nitrate solution, a chloride solution or a bromide solution of the metal ion. For example, if the metal ion is silver ion, the solution is selected from a silver nitrate solution, a silver chloride solution or a bromine. One of the silver solutions.
上述方法所製成之複合材料具有成膜性，且成膜後具 有可逆性，可回溶於溶液中；該金屬粒子之粒徑於成膜前的溶液內時，與成膜後回溶於溶液中時，其粒徑大小誤差小於7%。The composite material prepared by the above method has film forming property and is formed after film formation Reversible, can be dissolved back into the solution; when the particle size of the metal particle is in the solution before film formation, and the film is dissolved back into the solution after film formation, the particle size error is less than 7%.
上述方法所製成之複合材料，其中，該金屬粒子與脫層的矽酸鹽黏土之組成重量比介於0.5/99.5~50/50之間。The composite material prepared by the above method, wherein the composition ratio of the metal particles to the delaminated silicate clay is between 0.5/99.5 and 50/50.
藉此，利用一種可控制金屬粒子體積的奈米複合材料之製造方法，可以有效分散及穩定奈米金屬粒子，並藉由操控金屬粒子與脫層的矽酸鹽黏土複合材料之組成重量比，可得到不同體積的奈米金屬粒子。Thereby, by using a method for manufacturing a nano composite material capable of controlling the volume of the metal particles, the nano metal particles can be effectively dispersed and stabilized, and by controlling the composition ratio of the metal particles to the delaminated citrate clay composite material, Different volumes of nano metal particles are available.
以下茲就本發明所進行的實驗，說明各實施例所使用之原料及菌種來源，包括：The following is an experiment conducted by the present invention to explain the raw materials and strain sources used in the respective examples, including:
1.奈米矽片(Nanoscale Silicate Platelets，NSP)：可藉由脫層鈉離子型蒙脫土(Na+ -MMT)而得，製備方法可參見中華民國公告第I280261、I284138、I270529、577904及593480等號發明專利。1. Nanoscale Silicate Platelets (NSP): can be obtained by delamination of sodium ion montmorillonite (Na + -MMT). For the preparation method, please refer to the Republic of China Announcement Nos. I280261, I284138, I270529, 577904 and 593480 equal invention patent.
2.鈉離子型蒙脫土(sodium montmorillonite，Na+-MMT)：為層狀(smectic)矽酸鋁黏土，購自Nancor Co.。2. Sodium montmorillonite (Na+-MMT): a smectic aluminum silicate clay available from Nancor Co.
3.硝酸銀(AgNO3) ：Mw.=169.87 g/mol，購自J.T.Baker,Inc.。3. Silver nitrate (AgNO 3) : Mw. = 169.87 g/mol, available from JT Baker, Inc.
4.甲醇(MeOH)：95%，是一種弱還原劑，30~150℃ 時，可將銀離子緩慢還原成奈米銀。4. Methanol (MeOH): 95%, is a weak reducing agent, 30~150 °C Silver ions can be slowly reduced to nano silver.
5.乙醇(EtOH)：99.5%，是一種弱還原劑，30~150℃時，可將銀離子緩慢還原成奈米銀。5. Ethanol (EtOH): 99.5%, is a weak reducing agent, slowly reducing silver ions to nano silver at 30~150 °C.
6.異丙醇(isopropyl alcohol)：95%，是一種弱還原劑，30~150℃時，可將銀離子緩慢還原成奈米銀。6. Isopropyl alcohol: 95%, is a weak reducing agent, slowly reducing silver ions to nano silver at 30~150 °C.
7.硼氫化鈉(NaBH4 )：強還原劑，可快速還原銀離子。7. Sodium borohydride (NaBH 4 ): A strong reducing agent that can quickly reduce silver ions.
8. SMA：SMA3000-M2070，詳見Macromolecules 2007,40,1579-1584.8. SMA: SMA3000-M2070, see Macromolecules 2007, 40, 1579-1584.
9.聚乙烯醇(poly(vinyl acohol)，PVA)：Mw.=74800g/mo，鹼化度=98.5-99.2 mol%，購自Chang Chun Petrochemical Co.。9. Poly(vinyl acohol, PVA): Mw. = 74,800 g/mo, degree of alkalinity = 98.5-99.2 mol%, available from Chang Chun Petrochemical Co.
10.菌種：金黃色葡萄球菌(Staphylococcus aureus 71；431；10781)、化膿性鏈球菌(Streptococcus pyogenes Rob 193-2)、綠膿桿菌(Pseudomonas aeruginosa)以及大腸桿菌(Escherichia coli)皆為野外分離株，由中興大學生命科學系蘇鴻麟教授提供。10. Species: Staphylococcus aureus 71 (431; 1078), Streptococcus pyogenes Rob 193-2, Pseudomonas aeruginosa, and Escherichia coli are all isolated in the field. The strain was provided by Professor Su Honglin from the Department of Life Sciences of Zhongxing University.
11.標準菌液製備：將隔夜培養之菌液以1/100體積加入新鮮的Luria-Bertani(LB)液體培養基中培養約三小時，再使用分光光度計測量培養後菌液在OD600之吸光值，選擇OD600在0.4~0.6之間的菌液，即為標準菌液。11. Preparation of standard bacterial solution: The overnight culture solution was added to fresh Luria-Bertani (LB) liquid medium for about three hours in a volume of 1/100, and the absorbance of the culture solution after culturing at OD600 was measured using a spectrophotometer. Select the bacterial solution with OD600 between 0.4 and 0.6, which is the standard bacterial solution.
上述為本發明較佳實施例所提供的原料介紹，接下來描述許多實例以闡明本發明之實施方式，但這些實例僅作為描述用途，熟悉技術人士將可理解這些實例並非詳盡無疑且並不預期用來限制本發明的範圍。The above is a description of the materials provided in the preferred embodiments of the present invention, and many examples are described to illustrate the embodiments of the present invention, but these examples are for illustrative purposes only, and those skilled in the art will understand that these examples are not exhaustive and not expected. It is intended to limit the scope of the invention.
本發明金屬粒子/脫層的矽酸鹽黏土之較佳實施例以奈米銀/奈米矽片材料合成作說明，但亦可以不同黏土進行脫層後的所得的片狀黏土做載體，該些黏土可以為皂土、鋰皂土、蒙脫土、人工合成雲母、高嶺土、滑石、凹凸棒土、蛭石或層狀雙氫氧化物等。The preferred embodiment of the metal particle/delaminated citrate clay of the present invention is described by the synthesis of nano silver/nano bismuth material, but the flaky clay obtained by delamination of different clays can also be used as a carrier. Some clays may be bentonite, lithium bentonite, montmorillonite, synthetic mica, kaolin, talc, attapulgite, vermiculite or layered double hydroxide.
本發明實施例之金屬離子不限於銀離子，可以為金、銅、鐵或其他適當的金屬。且銀離子來源亦不限於硝酸銀，只要能適當地提供銀離子即可，例如，溴化銀溶液、氯化銀溶液、溴酸銀溶液或氯酸銀溶液。The metal ions of the embodiments of the present invention are not limited to silver ions and may be gold, copper, iron or other suitable metals. Further, the silver ion source is not limited to silver nitrate as long as it can appropriately supply silver ions, for example, a silver bromide solution, a silver chloride solution, a silver bromate solution or a silver chlorate solution.
本發明之較佳實施例奈米銀/奈米矽片材料合成，包括三個部分：A preferred embodiment of the invention is a nano silver/nano bismuth sheet material synthesis comprising three parts:
(一)乙醇還原銀離子及奈米矽片穩定分散奈米銀粒子。(1) Ethanol-reduced silver ions and nano-plates stably disperse nano-silver particles.
(二)調控銀離子/奈米矽片重量比以控制奈米銀粒子大小。(2) Adjusting the weight ratio of silver ion/nano bismuth tablets to control the size of nano silver particles.
(三)調控乙醇/水重量比有效控制奈米銀粒子大小。(3) Adjusting the ethanol/water weight ratio to effectively control the size of the nano silver particles.
銀離子/奈米矽片(Ag+ /NSP)重量比為7/93：首先，配製奈米矽片(NSP)溶液(46.5 g,2 wt% in water)和硝酸銀 (AgNO3 )溶液(0.11 g,1 wt%)，然後將2 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，並利用磁石攪拌半小時，且於反應裝置中通入氮氣，使系統維持在氮氣環境下避免氧化銀的生成；此外，並架設冷凝回流裝置避免高溫時乙醇揮發，接著再將1 wt%硝酸銀(AgNO3 )溶液緩慢滴入溶液中，繼續攪拌半小時，此時溶液為米白色，最後升溫至80℃，溶液會開始進行氧化還原反應，顏色慢慢產生變化，當反應3小時後，溶液就會呈現黃褐色，此反應過程中使用紫外線光譜儀(UV)隨時間監控奈米銀粒子的生成(特徵吸收波長為408 nm)，待吸收強度值不再變化反應即結束，此時利用抽氣過濾(使用whatman® 五號濾紙，Cat.No.1005 090)將多餘未反應之乙醇濾掉，再將產物從濾紙上刮下回溶至水中保存(3 wt%)，此產物稀釋至100 ppm呈現金黃色。圖2為還原銀離子隨時間變化的紫外線光譜儀(UV)吸收圖，由圖得知，反應3小時後，奈米粒子特徵吸收峰為408 nm，故可證明奈米銀粒子(AgNP)的生成。The weight ratio of silver ion/nano bismuth (Ag + /NSP) is 7/93: First, a solution of nano bismuth (NSP) solution (46.5 g, 2 wt% in water) and silver nitrate (AgNO 3 ) (0.11) g, 1 wt%), then placed a 2 wt% solution of nano-barium (NSP) in a 250 mL 3-neck round bottom flask, and then added ethanol solution (49.5 g) to make the final concentration of the solution 1 wt%. The magnet is stirred for half an hour, and nitrogen gas is introduced into the reaction device to maintain the system in a nitrogen atmosphere to avoid the formation of silver oxide; in addition, a condensing reflux device is set up to avoid evaporation of ethanol at a high temperature, and then 1 wt% silver nitrate is added ( The solution of AgNO 3 ) is slowly dropped into the solution and stirring is continued for half an hour. At this time, the solution is beige, and finally the temperature is raised to 80 ° C. The solution will start to undergo redox reaction, and the color will change slowly. After 3 hours of reaction, the solution will be It will be yellowish brown. During the reaction, the ultraviolet spectrometer (UV) is used to monitor the formation of nano silver particles (the characteristic absorption wavelength is 408 nm). The value of the absorption intensity is no longer changed, and the reaction ends. (using filter paper whatman ® V, Cat.No.1005 090) excess The reaction of the ethanol was filtered off, and the product solution to save scraped back (3 wt%) of water from the filter paper, this product was diluted to 100 ppm a golden yellow. Fig. 2 is a UV spectrometer (UV) absorption diagram of silver ions with reduced time. It can be seen from the figure that after 3 hours of reaction, the characteristic absorption peak of nanoparticle is 408 nm, so the formation of nano silver particles (AgNP) can be proved. .
同實施例1之實驗方式，控制不同銀離子/奈米矽片(Ag+ /NSP)重量比如表1所示。In the same manner as in the experimental example of Example 1, the weights of different silver ion/nanosheets (Ag + /NSP) were controlled as shown in Table 1.
配製奈米矽片(NSP)溶液(9.95 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(0.79 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(39.76 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。Prepare a solution of nano-barium (NSP) (9.95 g, 10 wt% in water) and a solution of silver nitrate (AgNO 3 ) (0.79 g, 1 wt% in water), then 10 wt% of nano-barium (NSP) The solution was placed in a 250 mL 3-neck round bottom flask, and water (39.76 g) was added, followed by ethanol solution (49.5 g) to give a final concentration of 1 wt%, and the water/ethanol weight ratio in the system was 1/1. And stirring with a magnet for half an hour, the subsequent reaction steps are the same as in Example 1.
配製奈米矽片(NSP)溶液(9.9 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(1.57 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(39.04 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。Prepare a solution of nano-barium (NSP) (9.9 g, 10 wt% in water) and silver nitrate (AgNO 3 ) (1.57 g, 1 wt% in water), then 10 wt% of nano-slices (NSP) The solution was placed in a 250 mL 3-neck round bottom flask, and water (39.04 g) was added, followed by ethanol solution (49.5 g) to give a final concentration of 1 wt%, and the water/ethanol weight ratio in the system was 1/1. And stirring with a magnet for half an hour, the subsequent reaction steps are the same as in Example 1.
配製奈米矽片(NSP)溶液(8.5 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(23.62 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(18.47 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。Prepare a solution of nano-barium (NSP) (8.5 g, 10 wt% in water) and silver nitrate (AgNO 3 ) (23.62 g, 1 wt% in water), then 10 wt% of nano-slices (NSP) The solution was placed in a 250 mL 3-neck round bottom flask, and water (18.47 g) was added, followed by ethanol solution (49.5 g) to give a final concentration of 1 wt%, and the water/ethanol weight ratio in the system was 1/1. And stirring with a magnet for half an hour, the subsequent reaction steps are the same as in Example 1.
配製奈米矽片(NSP)溶液(7.0 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(23.62 g,2 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(20.05 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。Prepare a solution of nano-barium (NSP) (7.0 g, 10 wt% in water) and silver nitrate (AgNO 3 ) (23.62 g, 2 wt% in water), then 10 wt% of nano-slices (NSP) The solution was placed in a 250 mL 3-neck round bottom flask, and water (20.05 g) was added, followed by ethanol solution (49.5 g) to give a final concentration of 1 wt%, and the water/ethanol weight ratio in the system was 1/1. And stirring with a magnet for half an hour, the subsequent reaction steps are the same as in Example 1.
配製奈米矽片(NSP)溶液(5.0 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(39.37 g,2 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(6.42 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。Prepare a solution of nano-barium (NSP) (5.0 g, 10 wt% in water) and silver nitrate (AgNO 3 ) (39.37 g, 2 wt% in water), then 10 wt% of nano-slices (NSP) The solution was placed in a 250 mL 3-neck round bottom flask, and water (6.42 g) was added, followed by ethanol solution (49.5 g) to give a final concentration of 1 wt%, and the water/ethanol weight ratio in the system was 1/1. And stirring with a magnet for half an hour, the subsequent reaction steps are the same as in Example 1.
固定Ag+ /NSP重量比為1/99，控制不同水(DI water)/乙醇(Ethanol)重量比如表1所示。The fixed Ag + /NSP weight ratio was 1/99, and the weight of DI water/Ethanol was controlled as shown in Table 1.
銀離子/奈米矽片(Ag+ /NSP)重量比為1/99：首先，配製奈米矽片(NSP)溶液(9.9 g,10 wt% in water)和硝酸 銀(AgNO3 )溶液(1.57 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(63.79 g)，再加入乙醇溶液(24.75 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為3/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。The weight ratio of silver ion/nanophthalate (Ag + /NSP) is 1/99: First, a solution of nano-barium (NSP) solution (9.9 g, 10 wt% in water) and silver nitrate (AgNO 3 ) is prepared (1.57 g, 1 wt% in water), then place a 10 wt% solution of nano-barium (NSP) in a 250 mL 3-neck round bottom flask, add water (63.79 g), and add ethanol solution (24.75 g) The final concentration of the solution was 1 wt%, and the water/ethanol weight ratio in the system was 3/1, and the magnet was stirred for half an hour, and the subsequent reaction steps were the same as in Example 1.
銀離子/奈米矽片(Ag+ /NSP)重量比為1/99：首先，配製奈米矽片(NSP)溶液(9.9 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(1.57 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(72.04 g)，再加入乙醇溶液(16,5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為5/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。The weight ratio of silver ion/nanophthalate (Ag + /NSP) is 1/99: First, a solution of nano-barium (NSP) solution (9.9 g, 10 wt% in water) and silver nitrate (AgNO 3 ) is prepared (1.57 g, 1 wt% in water), then place a 10 wt% nano-negative tablet (NSP) solution in a 250 mL 3-neck round bottom flask, add water (72.04 g), and add ethanol solution (16, 5 g), the final concentration of the solution was 1 wt%, and the water/ethanol weight ratio in the system was 5/1, and the magnet was stirred for half an hour, and the subsequent reaction steps were the same as in Example 1.
銀離子/奈米矽片(Ag+ /NSP)重量比為1/ 99：首先，配製奈米矽片(NSP)溶液(9.9 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(1.57 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(79.54 g)，再加入乙醇溶液(9 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為10/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。The weight ratio of silver ion/nanopyrene (Ag + /NSP) is 1/99: First, a solution of nano-slice (NSP) solution (9.9 g, 10 wt% in water) and silver nitrate (AgNO 3 ) is prepared (1.57 g, 1 wt% in water), then place 10 wt% of nano-salt (NSP) solution in a 250 mL 3-neck round bottom flask, add water (79.54 g), and add ethanol solution (9 g) The final concentration of the solution was 1 wt%, and the water/ethanol weight ratio in the system was 10/1, and the magnet was stirred for half an hour, and the subsequent reaction steps were the same as in Example 1.
銀離子/奈米矽片(Ag+ /NSP)重量比為1/99：首先，配製奈米矽片(NSP)溶液(9.9 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(1.57 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(88.54 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/0，並利用磁石攪拌半小時，後續之反應步驟同實施例1。The weight ratio of silver ion/nanophthalate (Ag + /NSP) is 1/99: First, a solution of nano-barium (NSP) solution (9.9 g, 10 wt% in water) and silver nitrate (AgNO 3 ) is prepared (1.57 g, 1 wt% in water), then put a 10 wt% solution of nano-barium (NSP) in a 250 mL 3-neck round bottom flask and add water (88.54 g) to make the final concentration of the solution 1 wt% While the water/ethanol weight ratio in the system was 1/0, and stirring with a magnet for half an hour, the subsequent reaction steps were the same as in Example 1.
本發明奈米銀/奈米矽片材料合成之較佳比較例包括三個部分：A preferred comparative example of the synthesis of the nanosilver/nano bismuth sheet material of the present invention comprises three parts:
(一)乙醇還原銀離子及蒙脫土(MMT)穩定分散奈米銀粒子(1) Ethanol reduction of silver ions and montmorillonite (MMT) stable dispersion of nano-silver particles
(二)不同溶劑(兼還原劑)還原銀離子及NSP穩定分散奈米銀粒子。(2) Different solvents (and reducing agents) reduce silver ions and NSP stably disperse the nano silver particles.
(三)NaBH4 還原銀離子及Polymer穩定分散奈米銀粒子(III) NaBH 4 reduction of silver ions and Polymer stable dispersion of nano silver particles
銀離子/蒙脫土(Ag+ /MMT)重量比為7/93：首先，先以去離子水膨潤蒙脫土(MMT)粉末，並配製蒙脫土(MMT)溶液(18.6 g,5 wt% in water)和硝酸銀(AgNO3 )溶液(11.02 g,1 wt% in water)，然後將5 wt%之蒙脫土(MMT)溶液 置於250 mL三頸圓底燒瓶中，並加入水(20.92 g)，再加入乙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/乙醇重量比為1/1，並利用磁石攪拌半小時，後續之反應步驟同實施例1。圖3為還原銀離子隨時間變化的紫外線光譜儀(UV)吸收圖，由圖得知，反應3小時後，奈米粒子特徵吸收峰為413nm，故可證明奈米銀粒子的生成。Silver ion / montmorillonite (Ag + /MMT) weight ratio of 7 / 93: First, first demineralized montmorillonite (MMT) powder with deionized water, and prepare montmorillonite (MMT) solution (18.6 g, 5 wt % in water) and silver nitrate (AgNO 3 ) solution (11.02 g, 1 wt% in water), then place a 5 wt% montmorillonite (MMT) solution in a 250 mL 3-neck round bottom flask and add water ( 20.92 g), add ethanol solution (49.5 g) to make the final concentration of the solution 1 wt%, and the water/ethanol weight ratio in the system is 1/1, and stir with magnet for half an hour. The subsequent reaction steps are the same as in the first embodiment. . Fig. 3 is a UV spectrometer (UV) absorption diagram of the reduced silver ions as a function of time. It is known from the figure that after 3 hours of reaction, the characteristic absorption peak of the nanoparticles is 413 nm, so that the formation of nano silver particles can be confirmed.
改變溶劑，使用甲醇及異丙醇當溶劑並還原銀離子。Change the solvent, use methanol and isopropanol as solvent and reduce silver ions.
銀離子/奈米矽片(Ag+ /NSP)重量比為7/93：首先，配製奈米矽片(NSP)溶液(9.3 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(11.02 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(30.22 g)，再加入甲醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/甲醇重量比為1/1，並利用磁石攪拌半小時，且於反應裝置中通入氮氣，使系統維持在氮氣環境下避免氧化銀的生成；此外，並架設冷凝回流裝置避免高溫時甲醇揮發，接著再將1 wt%硝酸銀(AgNO3 )溶液緩慢滴入溶液中，繼續攪拌半小時，此時溶液為米白色，最後升溫至60℃，溶液會開始進行氧化還 原反應，顏色慢慢產生變化，當反應3小時後，溶液就會呈現深黃褐色，此反應過程中使用紫外線光譜儀(UV)隨時間監控奈米銀粒子的生成(特徵吸收波長為420 nm)，待吸收強度值不再變化反應即結束，此時利用抽氣過濾(使用whatman® 五號濾紙，Cat.No.1005 090)將多餘未反應之甲醇濾掉，再將產物從濾紙上刮下回溶至水中保存(3 wt%)，此產物稀釋至100 ppm呈現金黃色。圖4為還原銀離子隨時間變化的紫外線光譜儀(UV)吸收圖，由圖得知，反應12小時後，奈米粒子特徵吸收峰為420 nm，故可證明奈米銀粒子的生成。Silver ion/nano bismuth (Ag + /NSP) weight ratio is 7/93: First, prepare nano sputum (NSP) solution (9.3 g, 10 wt% in water) and silver nitrate (AgNO 3 ) solution (11.02) g, 1 wt% in water), then place a 10 wt% solution of nano-barium (NSP) in a 250 mL 3-neck round bottom flask, add water (30.22 g), and add methanol solution (49.5 g) The final concentration of the solution is 1 wt%, and the water/methanol weight ratio in the system is 1/1, and the magnet is stirred for half an hour, and nitrogen is introduced into the reaction device to maintain the system in a nitrogen atmosphere to avoid silver oxide. In addition, a condensing reflux device is installed to avoid methanol volatilization at high temperature, and then a 1 wt% silver nitrate (AgNO 3 ) solution is slowly dropped into the solution, and stirring is continued for half an hour, at which time the solution is beige and finally heated to 60 ° C. The solution will start to undergo redox reaction, and the color will change slowly. When the reaction is carried out for 3 hours, the solution will be dark brown. During the reaction, the formation of nano silver particles is monitored by ultraviolet spectrometer (UV). The absorption wavelength is 420 nm), and the value of the absorption intensity does not change, the reaction ends. Using suction filtration (using a filter paper whatman ® V, Cat.No.1005 090) the unreacted excess of methanol was filtered off, the product was scraped from the filter back to the storage solution (3 wt%) in water, the product was diluted It is golden yellow to 100 ppm. Fig. 4 is a UV spectrometer (UV) absorption diagram of the reduced silver ions as a function of time. It is known from the figure that after 12 hours of reaction, the characteristic absorption peak of the nanoparticle is 420 nm, so that the formation of nano silver particles can be confirmed.
銀離子/奈米矽片(Ag+ /NSP)重量比為7/93：首先，配製NSP溶液(9.3 g,10 wt% in water)和硝酸銀(AgNO3 )溶液(11.02 g,1 wt% in water)，然後將10 wt%之奈米矽片(NSP)溶液置於250 mL三頸圓底燒瓶中，並加入水(30.22 g)，再加入異丙醇溶液(49.5 g)，使溶液最終濃度為1 wt%，而系統中水/異丙醇重量比為1/1，並利用磁石攪拌半小時，且於反應裝置中通入氮氣，使系統維持在氮氣環境下避免氧化銀的生成；此外，並架設冷凝回流裝置避免高溫時甲醇揮發，接著再將1 wt%硝酸銀(AgNO3 )溶液緩慢滴入溶液中，繼續攪拌半小時，此時溶液為米白色，最後升溫至80℃，溶液會開始進行氧化還原反應，顏色慢慢產生變化，當反應2小時後，溶液就會呈現深黃褐 色，此反應過程中使用紫外線光譜儀(UV)隨時間監控奈米銀粒子的生成(特徵吸收波長為420 nm)，待吸收強度值不再變化反應即結束，此時利用抽氣過濾(使用whatman® 五號濾紙，Cat.No.1005 090)將多餘未反應之甲醇濾掉，再將產物從濾紙上刮下回溶至水中保存(3 wt%)，此產物稀釋至100 ppm呈現金黃色。圖5為還原銀離子隨時間變化的紫外線光譜儀(UV)吸收圖，由圖得知，反應8小時後，奈米粒子特徵吸收峰為420 nm，故可證明奈米銀粒子的生成。Silver ion/nanophthalate (Ag + /NSP) weight ratio is 7/93: First, prepare NSP solution (9.3 g, 10 wt% in water) and silver nitrate (AgNO 3 ) solution (11.02 g, 1 wt% in Water), then place a 10 wt% solution of nano-barium (NSP) in a 250 mL 3-neck round bottom flask, add water (30.22 g), and add isopropanol solution (49.5 g) to make the solution final. The concentration is 1 wt%, and the water/isopropanol weight ratio in the system is 1/1, and the magnet is stirred for half an hour, and nitrogen gas is introduced into the reaction device to maintain the system in a nitrogen atmosphere to avoid the formation of silver oxide; In addition, a condensing reflux device is set up to avoid methanol evaporation at high temperature, and then 1 wt% silver nitrate (AgNO 3 ) solution is slowly dropped into the solution, and stirring is continued for half an hour. At this time, the solution is beige, and finally the temperature is raised to 80 ° C. The oxidation-reduction reaction will start, and the color will change slowly. When the reaction is carried out for 2 hours, the solution will be dark brown. During the reaction, the formation of nano-silver particles is monitored by ultraviolet spectrometer (UV) over time (characteristic absorption wavelength). At 420 nm), the value of the absorbed intensity no longer changes, and the reaction ends. Gas is filtered (filter paper whatman ® V, Cat.No.1005 090) of the unreacted excess methanol was filtered off, and the product solution to save scraped back (3 wt%) of water from the filter paper, this product was diluted to 100 Ppm is golden yellow. Fig. 5 is a UV spectrometer (UV) absorption diagram of the reduced silver ions as a function of time. It is known from the figure that after 8 hours of reaction, the characteristic absorption peak of the nanoparticles is 420 nm, so that the formation of nano-silver particles can be confirmed.
以高分子型分散劑(SMA)取代奈米矽片(NSP)去作奈米銀粒子(AgNP)的分散。The nano-particles (NSP) were replaced by a polymeric dispersant (SMA) to disperse the nano-silver particles (AgNP).
銀離子/高分子型分散劑(Ag+ /SMA)重量比為7/93：首先，秤取SMA3000-M2070(0.93 g)和硝酸銀(0.11 g)，分別溶於25 g去離子水中，再將此二溶液混合置於250 mL三頸圓底燒瓶中，並利用磁石均勻攪拌半小時，且於反應裝置中通入氮氣，使系統維持在氮氣環境下避免氧化銀的生成；接著配置硼氫化鈉(NaBH4 )溶液，取0.03 g溶於50 g去離子水中，再逐滴緩慢加入溶液中，此時，系統濃度為1 wt%，且溶液會開始進行氧化還原反應，顏色慢慢產生變化，當反應3小時後，溶液就會呈現深 咖啡色，此反應過程中使用紫外線光譜儀(UV)隨時間監控奈米銀粒子的生成(特徵吸收波長為390 nm)，待吸收強度值不再變化反應即結束(約3~4 H)，即可獲得1 wt%之奈米銀粒子/高分子型分散劑(AgNP/SMA)水溶液。此產物稀釋至100 ppm呈現金黃色。The weight ratio of silver ion/polymer dispersant (Ag + /SMA) is 7/93: First, weigh SMA3000-M2070 (0.93 g) and silver nitrate (0.11 g), respectively, dissolved in 25 g of deionized water, and then The two solutions were mixed and placed in a 250 mL three-necked round bottom flask, and uniformly stirred by a magnet for half an hour, and nitrogen gas was introduced into the reaction apparatus to maintain the system under a nitrogen atmosphere to avoid the formation of silver oxide; then, sodium borohydride was disposed. (NaBH 4 ) solution, take 0.03 g dissolved in 50 g of deionized water, and slowly add to the solution dropwise. At this time, the system concentration is 1 wt%, and the solution will start to undergo redox reaction, and the color will change slowly. After 3 hours of reaction, the solution will be dark brown. During the reaction, the formation of nano-silver particles (the characteristic absorption wavelength is 390 nm) is monitored with time using an ultraviolet spectrometer (UV), and the absorption intensity value is no longer changed. At the end (about 3 to 4 H), a 1 wt% aqueous solution of nano silver particles/polymer type dispersant (AgNP/SMA) can be obtained. This product was diluted to 100 ppm to give a golden yellow color.
上述為本發明較佳實施例及比較例之材料配置與製造方法，接著詳細介紹本發明對奈米銀粒子熱穩定性探討之實施方式，其測試方式主要分為三個部分：The above is a material configuration and manufacturing method of the preferred embodiment and the comparative example of the present invention, and then the embodiment of the present invention for discussing the thermal stability of the nano silver particles is described in detail. The test method is mainly divided into three parts:
(一)紫外線光譜儀(UV)照射(1) Ultraviolet spectrometer (UV) irradiation
將測試樣品配置為0.05 wt%，並置於紫外光燈(UVGL-58 Handheld UV lamp,254/365 nm,6-Watt,115 V~60 Hz,0.12 Amps)下照射4小時，利用紫外光-可見光光譜儀(Hitachi U-4100)測量其吸收鋒位置是否紅移。The test sample was configured to be 0.05 wt% and placed under UV light (UVGL-58 Handheld UV lamp, 254/365 nm, 6-Watt, 115 V~60 Hz, 0.12 Amps) for 4 hours, using ultraviolet-visible light. The spectrometer (Hitachi U-4100) measures whether the position of its absorption front is red-shifted.
(二)熱處理(2) Heat treatment
將測試樣品配置為1 wt%，並置於80℃油浴中加熱8 H，利用紫外光-可見光光譜儀(Hitachi U-4100)測量其吸收鋒位置是否紅移，並使用穿透式電子顯微鏡TEM(JOEL JEM-1230 electron microscope operating at 100 kV and with a Gatan DualVision CCD Camera)觀察粒子聚集情形。The test sample was configured to be 1 wt%, and placed in an 80 ° C oil bath to heat 8 H, and its absorption front position was measured by an ultraviolet-visible spectrometer (Hitachi U-4100) to be red-shifted, and a transmission electron microscope TEM ( JOEL JEM-1230 electron microscope operating at 100 kV and with a Gatan DualVision CCD Camera) observed particle aggregation.
(三)膜的穩定性(可逆性)(III) Stability of the membrane (reversibility)
(a)純無機膜-銀粒子/奈米矽片(Ag/NSP)膜和銀粒子/蒙脫土(Ag/MMT)膜(a) Pure inorganic film - silver particle / nano slab (Ag / NSP) film and silver particle / montmorillonite (Ag / MMT) film
將測試樣品配置為1 wt%，取適量滴於載玻片上置於60℃烘箱中成膜，待測完紫外線光譜儀(UV)吸收值後，再以去離子水溶解此膜，利用紫外線-可見光光譜儀(Hitachi U-4100)測量其成膜前後溶液之吸收鋒位置是否有所變化。The test sample was configured to be 1 wt%, and an appropriate amount was dropped on a glass slide to form a film in an oven at 60 ° C. After the ultraviolet spectrometer (UV) absorption value was measured, the film was dissolved in deionized water to utilize ultraviolet-visible light. The spectrometer (Hitachi U-4100) measures whether the position of the absorption front of the solution changes before and after film formation.
(b)無機/有機膜-銀粒子/奈米矽片/聚乙烯醇 (Ag/NSP/PVA)膜(b) Inorganic/organic film-silver particles/nanophthalate/polyvinyl alcohol (Ag/NSP/PVA) film
將測試樣品配置為1 wt%，並混入1 wt%聚乙烯醇(PVA)，取適量平鋪於培養皿上置於60℃烘箱中成膜，待測完紫外線光譜儀(UV)吸收值後，再以去離子水溶解此膜，利用紫外線-可見光光譜儀(Hitachi U-4100)測量成膜前後溶液之吸收鋒位置是否有所變化。The test sample was configured to be 1 wt%, and mixed with 1 wt% polyvinyl alcohol (PVA), and the appropriate amount was placed on a petri dish and placed in a 60 ° C oven to form a film. After the UV spectrometer (UV) absorption value was measured, The film was dissolved in deionized water, and the position of the absorption front of the solution before and after the film formation was measured by an ultraviolet-visible spectrometer (Hitachi U-4100).
以上(一)~(二)之測試主要使用實施例1、比較例1、比較例4；而(三)-a之測試主要使用實施例1及比較例1；(三)-b之測試主要使用實施例1、實施例3、實施例4、實施例5及實施例6。The tests of (1) to (2) above mainly use Example 1, Comparative Example 1 and Comparative Example 4; and the tests of (3)-a mainly use Example 1 and Comparative Example 1; (3)-b test mainly Example 1, Example 3, Example 4, Example 5, and Example 6 were used.
接著更進一步探討本發明之奈米銀粒子的抗菌能力，其測試方式如下所述：奈米銀粒子/無機黏土配成不同濃度於10 ml的LB液態培養基，加入100 λ的標準菌液，1×105 CFU/ml(colony formation unit/ml)。在37℃培養3和24小時後，取溶液出來稀釋至適當倍數後，取50 λ以滅菌後的玻璃珠均勻塗抹於10 mm LB固態培養基上。經過37℃培養24小時後計算其菌落數。Next, the antibacterial ability of the nano silver particles of the present invention is further explored, and the test method is as follows: the nano silver particles/inorganic clay are formulated into LB liquid medium with different concentrations in 10 ml, and the standard bacterial liquid of 100 λ is added, 1 ×10 5 CFU/ml (colony formation unit/ml). After incubating at 37 ° C for 3 and 24 hours, the solution was diluted to an appropriate multiple, and 50 λ was taken and the sterilized glass beads were evenly spread on a 10 mm LB solid medium. The number of colonies was calculated after 24 hours of incubation at 37 °C.
測試樣品主要分為三個部分：The test sample is mainly divided into three parts:
(一)不同穩定劑穩定之奈米銀粒子(AgNP)抗菌比較--奈米銀粒子/奈米矽片(AgNP/NSP)和奈米銀粒子/蒙脫土(AgNP/MMT)(I) Antimicrobial comparison of nano silver particles (AgNP) stabilized by different stabilizers--Nano silver particles/nano bismuth tablets (AgNP/NSP) and nano silver particles/montmorillonite (AgNP/MMT)
(二)不同奈米銀粒子(AgNP)粒子大小抗菌比較(包 含四株菌種：大腸桿菌、綠膿桿菌、金黃色葡萄球菌及化膿性鏈球菌；而比較之樣品奈米銀粒子/奈米矽片(AgNP/NSP)比例由1/99~50/50共五支)(B) Antibacterial comparison of particle size of different nano silver particles (AgNP) Contains four strains: Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Streptococcus pyogenes; and the ratio of samples of nano silver particles/nanopyrene tablets (AgNP/NSP) is 1/99~50/50 A total of five)
(三)局部濃度差異之抗菌比較(奈米銀粒子/奈米矽片(AgNP/NSP)比例：0.5/99.5 vs.1/99)(III) Antibacterial comparison of local concentration differences (nano silver particles/nanopyrene tablets (AgNP/NSP) ratio: 0.5/99.5 vs. 1/99)
以上(一)之樣品為實施例1和比較例1；而(二)之樣品為實施例1、實施例3、實施例4、實施例5及實施例6；至於(三)之樣品則為實施例2及實施例3。The samples of (1) above are Example 1 and Comparative Example 1; the samples of (2) are Examples 1, 3, 4, 5 and 6; and the samples of (3) are Example 2 and Example 3.
上述為本發明之熱穩定性及抗菌測試的較佳實施方式，接著說明實驗結果及分析討論。The above is a preferred embodiment of the thermal stability and antibacterial test of the present invention, followed by an explanation of the experimental results and analysis.
由實施例1與比較例1-3之穿透式顯微鏡(TEM)分析結果可知，使用乙醇當還原劑(如圖6(a))所得之奈米銀粒子粒徑分佈較用甲醇(如圖6(c))及異丙醇(如圖6(d))當還原劑來得均勻；另外，使用脫層之黏土(奈米矽片，NSP)穩定分散銀粒子(如圖6(a))效果較優於未脫層之黏土(蒙脫土，MMT)(如圖6(b)所示)，穩定在蒙脫土(MMT)表面之奈米銀粒子之數量相對也較少，導致許多自由之奈米銀粒子在蒙脫土(MMT)外圍發生聚集現象，因此本發明之奈米銀粒子(AgNP)所選用之還原劑(乙醇)與穩定劑(奈米矽片)具有較優異的穩定能力。From the results of the transmission microscope (TEM) analysis of Example 1 and Comparative Example 1-3, it was found that the particle size distribution of the nano silver particles obtained by using the reducing agent (as shown in Fig. 6 (a)) was higher than that of methanol. 6(c)) and isopropanol (Fig. 6(d)) when the reducing agent is evenly obtained; in addition, the delaminated clay (nanopyrene, NSP) is used to stably disperse the silver particles (Fig. 6(a)) The effect is better than the undelaminated clay (montmorillonite, MMT) (as shown in Figure 6 (b)), the number of nano silver particles stabilized on the surface of montmorillonite (MMT) is relatively small, resulting in many The free nano silver particles are aggregated around the montmorillonite (MMT), so the reducing agent (ethanol) and the stabilizer (nanopyrene) selected for the nano silver particles (AgNP) of the present invention are excellent. Stability ability.
利用奈米矽片來穩定分散奈米銀粒子，可使其具有高穩定性，在紫外線光譜儀(UV)光源照射及熱處理之下，皆能保持其粒子大小而不會聚集(實施例1)；相較而言，比較例4，使用高分子型分散劑來穩定分散奈米銀粒子效果有限，且會導致銀粒子聚集，其現象可藉由紫外線-可見光光譜儀(UV)分析，由波峰之紅移變化與否來判定聚集程度，如表2所示。同時，亦藉由圖7之穿透式顯微鏡(TEM)分析來驗證此結果。The use of nano-ruthenium tablets to stably disperse nano-silver particles can make them have high stability, and can maintain their particle size without being aggregated under ultraviolet light source (UV) light source irradiation and heat treatment (Example 1); In comparison, in Comparative Example 4, the use of a polymeric dispersant to stabilize the dispersion of nano-silver particles has a limited effect and causes aggregation of silver particles, which can be analyzed by ultraviolet-visible spectrometer (UV), from the peak of the peak. Change the degree of aggregation to determine the degree of aggregation, as shown in Table 2. At the same time, this result was also verified by the transmission microscope (TEM) analysis of FIG.
黏土型穩定劑穩定效果皆優於高分子型穩定劑，而本發明之脫層黏土(NSP)穩定分散效果更優於一般黏土(蒙脫土(MMT)，由實施例1及比較例1，當進行穩定性測試時發現，奈米銀粒子/奈米矽片(AgNP/NSP)經成膜處理後，再次回溶於水溶液中，可發現奈米銀粒子/奈米矽片(AgNP/NSP)之特徵吸收峰可再回到原始溶液之狀態，此現象證明奈米銀粒子具有可逆之能力，即使在成膜過程中發生聚集現象；相較而言，奈米銀粒子/蒙脫土 (AgNP/MMT)就不具此能力。圖8為其紫外線-可見光光譜儀分析結果，由吸收峰的位置來斷定是否具有可逆行為。The stability effect of clay-type stabilizers is better than that of polymer-type stabilizers, and the stratified clay (NSP) of the present invention has better stable dispersion effect than ordinary clay (montmorillonite (MMT), from Example 1 and Comparative Example 1, When the stability test was carried out, it was found that the nano silver particles/nano bismuth tablets (AgNP/NSP) were dissolved in the aqueous solution after being formed into a film, and nano silver particles/nano bismuth tablets (AgNP/NSP) were found. The characteristic absorption peak can be returned to the state of the original solution. This phenomenon proves that the nano silver particles have the reversible ability to aggregate even during film formation; in comparison, nano silver particles/montmorillonite (AgNP/MMT) does not have this ability. Fig. 8 is a result of analysis by the ultraviolet-visible spectrometer, and it is judged by the position of the absorption peak whether or not there is reversible behavior.
利用奈米矽片表面的離子吸附作用力，以片狀矽片分散球狀銀粒子而有效穩定奈米銀粒子於矽片表面，再依照不同銀離子/奈米矽片(Ag+ /NSP)重量比例進行反應(如表1實施例1~6)，可獲得不同體積大小的奈米級銀粒子水溶液，而控制該銀粒子之粒徑範圍為3.6 nm至35 nm，如圖9所示。此外，利用調控去離子水/乙醇(DI water/Ethanol)重量比例進行反應(如表1實施例1、7~10)，亦可有效控制奈米銀粒子之體積大小，且當比例為3/ 1時(實施例7)，可獲得最小的粒子體積，其粒徑約為3.3 nm，如圖10所示。而本發明所有合成之奈米銀粒子(AgNP)之粒徑統整結果如表3所示。Using the ion-adsorbing force on the surface of the nanosheet, the spherical silver particles are dispersed in the flaky enamel to effectively stabilize the nano-silver particles on the surface of the enamel, and then according to different silver ions/nano sheets (Ag + /NSP) The reaction was carried out in a weight ratio (as in Examples 1 to 6 in Table 1), and aqueous solutions of nano-sized silver particles of different volume sizes were obtained, and the particle size of the silver particles was controlled to be in the range of 3.6 nm to 35 nm, as shown in FIG. In addition, the reaction can be carried out by adjusting the weight ratio of DI water/Ethanol (as in Examples 1, 7-10 of Table 1), and the volume of the nano silver particles can be effectively controlled, and when the ratio is 3/ At 1 o'clock (Example 7), the smallest particle volume was obtained with a particle size of about 3.3 nm, as shown in FIG. The results of the particle size integration of all the synthesized nano silver particles (AgNP) of the present invention are shown in Table 3.
此外，更進一步測試不同粒子大小之奈米銀粒子(AgNP)其可逆行為之差異，我們發現當銀離子/奈米矽片(Ag+ /NSP)重量比例為1/99~15/85時(實施例1、3、4)，其奈米銀粒子(AgNP)的穩定性尤佳，於穩定性測試時，其經成膜處理後，再次回溶於水溶液中，可發現奈米銀粒子/奈米矽片(AgNP/NSP)之特徵吸收峰可再回到原始溶液之狀態，此現象證明奈米銀粒子具有可逆之能力，即使在成膜過程中發生聚集現象；相較而言，當銀離子/奈米矽片(Ag+ /NSP)重量比例為30/70~50/50時(實施例5、6)，可逆能力相對較差，但仍然比奈米銀粒子/蒙脫土(AgNP/MMT)佳(比較例1)。圖11為其紫外線-可見光光譜儀分析結果，由吸收峰的位置來斷定是否具有可逆行為。而圖12為其穿透式顯微鏡(TEM)驗證之結果，可證實其奈米銀粒子(AgNP)粒子體積大小經成膜處理後仍可 逆，成膜前與回溶後之奈米銀粒子(AgNP)體積差異小。In addition, we further tested the difference in reversible behavior of nano-silver particles (AgNP) with different particle sizes. We found that when the weight ratio of silver ion/nanopyrene (Ag + /NSP) is 1/99~15/85 ( In Examples 1, 3, and 4), the stability of the nano silver particles (AgNP) is particularly good. When the film is subjected to a filming treatment, it is again dissolved in an aqueous solution, and nano silver particles can be found. The characteristic absorption peak of the nano-ply film (AgNP/NSP) can be returned to the state of the original solution. This phenomenon proves that the nano-silver particles have the reversible ability to aggregate even during film formation; in comparison, when When the weight ratio of silver ion/nanopyrene (Ag + /NSP) is 30/70~50/50 (Examples 5 and 6), the reversible ability is relatively poor, but still better than nano silver particles/montmorillonite (AgNP/ MMT) is good (Comparative Example 1). Fig. 11 shows the results of analysis by the ultraviolet-visible spectrometer, and it is judged whether or not there is reversible behavior from the position of the absorption peak. Figure 12 shows the results of a transmission microscope (TEM). It can be confirmed that the nano-silver particle (AgNP) particle size is reversible after film formation, and the nano-silver particles before and after film formation ( AgNP) has a small difference in volume.
本發明之奈米銀粒子/奈米矽片(AgNP/NSP)複合材料亦具有優越之抗菌能力，圖13顯示實施例1與比較例1之奈米銀粒子(AgNP)樣品溶液進行抗菌實驗之結果，我們發現奈米銀粒子/奈米矽片(AgNP/NSP)複合材料(實施例1)具有優越之抗菌能力，在銀粒子濃度為10 ppm時，接觸3小時即完全殺菌(大腸桿菌)，相較而言，奈米銀粒子/蒙脫土(AgNP/MMT)複合材料(比較例1)在銀粒子濃度為10 ppm時，在接觸6小時之內還具有抑菌能力，但在此之後抑菌能力消失，菌則又開始增生，材料失去作用。The nano silver particle/nano wafer (AgNP/NSP) composite of the present invention also has superior antibacterial ability, and FIG. 13 shows the solution of the nano silver particle (AgNP) sample of Example 1 and Comparative Example 1 for antibacterial experiment. As a result, we found that the nano silver particle/nano bismuth (AgNP/NSP) composite (Example 1) has superior antibacterial ability, and when the concentration of silver particles is 10 ppm, it is completely sterilized after exposure for 3 hours (E. coli). In comparison, the nano silver particle/montmorillonite (AgNP/MMT) composite (Comparative Example 1) has antibacterial ability within 6 hours of contact at a silver particle concentration of 10 ppm, but here After that, the antibacterial ability disappeared, and the bacteria began to proliferate again, and the material lost its effect.
此外，我們比照上述奈米銀粒子/奈米矽片(AgNP/NSP)複合材料之最低殺菌濃度(10 ppm)，固定銀粒子之濃度為10 ppm，比較不同粒子大小之奈米銀粒子(AgNP)(實施例1、3~6)抗菌差異，發現當粒子越小其相對抗大腸桿菌之能力越佳，而針對其他菌株(綠膿桿菌、金黃色葡萄球菌及化膿性鏈球菌)，無論是革蘭氏陰性菌或陽性菌，亦可得到相同之結果，如圖14所示，而更詳細之抗菌數據列於表4。因此，由本發明之抗菌結果發現，我們可以藉由操控不同奈米銀粒子/奈米矽片(AgNP/NSP)之比例，進而得到材料不同的抗菌能力，因此可證明抗菌能力之差異主要為粒子體積大小不同造 成。而圖15、16分別為本發明之奈米銀粒子/奈米矽片(AgNP/NSP)複合材料與大腸桿菌及金黃色葡萄球菌接觸後，隨時間利用掃描式電子顯微鏡(SEM)觀測其菌株型態上之變化。In addition, we compared the minimum bactericidal concentration (10 ppm) of the above-mentioned nano silver particle/nano bismuth (AgNP/NSP) composite, and fixed silver particles at a concentration of 10 ppm to compare nanoparticle particles of different particle sizes (AgNP). (Examples 1, 3-6) Antibacterial differences, found that the smaller the particles, the better their ability to resist E. coli, and against other strains (Pseudomonas aeruginosa, Staphylococcus aureus and Streptococcus pyogenes), whether Gram-negative bacteria or positive bacteria can also give the same results, as shown in Figure 14, and more detailed antibacterial data are listed in Table 4. Therefore, it has been found from the antibacterial results of the present invention that we can obtain different antibacterial abilities of the materials by manipulating the ratio of different nano silver particles/nano bismuth tablets (AgNP/NSP), and thus it can be confirmed that the difference in antibacterial ability is mainly particles. Different size to make. 15 and 16 respectively, the nano silver/nip sheet (AgNP/NSP) composite of the present invention was contacted with Escherichia coli and Staphylococcus aureus, and the strain was observed by scanning electron microscopy (SEM) over time. The change in type.
再者，為了更進一步展現NSP在本發明中所具備的獨特性，我們選擇了兩個奈米銀粒子(AgNP)粒子體積大小相近之材料，奈米銀粒子/奈米矽片(AgNP/NSP)重量比分別為1/99和0.5/99.5(實施例2和3)，進行抗菌測試，我們發現當奈米矽片(NSP)含量較高時(0.5/99.5)，其抗菌能力相對也較高，如圖17所示。此發現也驗證了本發明在基於相同奈米銀粒子(AgNP)粒子體積大小狀況下，含有較高比例的奈米矽片(NSP)之材料具備較高的殺菌功效，其主要殺菌機制歸咎於奈米矽片(NSP)本身具高的表面積和密集的離子表面電荷，容易貼附至菌體表面，使較多的奈米銀粒子(AgNP)有機會接觸到細菌表面，以致 材料具有較高的殺菌能力。因此，本發明之獨特性就在於可藉由調控奈米銀粒子/奈米矽片(AgNP/NSP)重量比，來得到不同奈米矽片(NSP)含量之奈米銀粒子/奈米矽片(AgNP/NSP)複合材料，進而增強材料之抗菌能力。Furthermore, in order to further demonstrate the uniqueness of NSP in the present invention, we have selected two nano silver particle (AgNP) particles with similar volume, nano silver particles/nano wafers (AgNP/NSP). The weight ratio was 1/99 and 0.5/99.5 (Examples 2 and 3), and the antibacterial test was carried out. We found that when the content of nano-slice (NSP) is high (0.5/99.5), the antibacterial ability is relatively high. High, as shown in Figure 17. This finding also verifies that the present invention has a high bactericidal effect on a material containing a relatively high proportion of nano-slice tablets (NSP) based on the size of the same nano-silver particle (AgNP) particle size, and the main bactericidal mechanism is attributed to The nano-slices (NSP) itself have a high surface area and a dense ionic surface charge, which is easy to attach to the surface of the bacteria, so that more nano-silver particles (AgNP) have the opportunity to contact the surface of the bacteria. The material has a high bactericidal ability. Therefore, the uniqueness of the present invention is that nano-silver particles/nanophthalenes with different nano-slices (NSP) content can be obtained by adjusting the weight ratio of nano-silver particles/nanopyrene tablets (AgNP/NSP). The sheet (AgNP/NSP) composite material enhances the antibacterial ability of the material.
以上所述僅為本發明較佳可行實施例而已，舉凡應用本發明說明書及申請專利範圍所為之等效結構及製作方法變化，理應包含在本發明之專利範圍內。The above description is only for the preferred embodiments of the present invention, and the equivalent structures and manufacturing methods of the present invention and the scope of the patent application are intended to be included in the scope of the present invention.
1‧‧‧鈉離子型蒙脫土1‧‧‧Sodium ion montmorillonite
2‧‧‧高分子2‧‧‧ Polymer
3‧‧‧奈米矽片3‧‧‧Nano film
圖1為示意圖，顯示奈米矽片之製備以及奈米銀粒子的穩定形成；圖2為紫外線-可見光光譜圖，顯示以乙醇還原之奈米銀粒子/奈米矽片(AgNP/NSP，7/93)溶液；圖3為紫外線-可見光光譜圖，顯示以乙醇還原之奈米銀粒子/蒙脫土(AgNP/MMT，7/93)溶液；圖4為紫外線-可見光光譜圖，顯示以甲醇還原之奈米銀粒子/奈米矽片(AgNP/NSP，7/93)溶液；圖5為紫外線-可見光光譜圖，顯示以異丙醇還原之奈米銀粒子/奈米矽片(AgNP/NSP，7/93)溶液；圖6為穿透式電子顯微鏡(TEM)圖，顯示分析粒子大小分佈之差異(a)奈米銀粒子/奈米矽片(AgNP/NSP)_乙醇還原(b)奈米銀粒子/蒙脫土(AgNP/MMT)_乙醇還原(c)奈米銀粒子/奈米矽片(AgNP/NSP)_甲醇還原(d)奈米銀粒子/奈米矽片(AgNP/NSP)_異丙醇還原；圖7為穿透式電子顯微鏡(TEM)圖，顯示加熱處理前後粒子大小之變化(a)(d)Ag/SMA3000-M2070(b)(e)Ag/MMT(c)(f)Ag/NSP.(a)~(c)加熱前；(d)~(f)加熱8 H後；圖8為紫外線-可見光光譜圖，顯示成膜處理後再回溶之吸收峰位置變化(a)AgNP/Clay外觀圖(b)AgNP/NSP之UV分析圖(c)AgNP/MMT之紫外線分析圖(黑線為成膜前之溶液；紅線為膜態；藍線為在回溶後 之溶液)；圖9 為穿透式電子顯微鏡(TEM)圖，顯示奈米銀粒子/奈米矽片(AgNP/NSP)之不同重量比的平均粒徑大小(a)0.5/99.5(P3.6)(b)1/99(P3.8),(c)7/93(P5),(d)15/85(P9),(e)30/70(P17)和(f)50/50(P35)；圖10為穿透式電子顯微鏡(TEM)圖，顯示銀粒子於乙醇/水(EtOH/H2 O)之不同重量比的平均粒徑大小(a)1/1，(b)3/1，(c)5/1，(d)10/1，(e)1/0，另外(f)為不同乙醇含量之平均粒徑的比較；圖11為紫外線-可見光光譜圖，顯示奈米銀粒子(AgNP)於不同粒徑大小時的可逆性能力(a)奈米銀粒子(AgNP)成膜後的照片(b)溶液的光譜圖(c)膜的光譜圖(d)再回溶後溶液光譜圖；圖12為紫外線-可見光光譜圖及穿透式電子顯微鏡(TEM)圖，顯示奈米銀粒子(AgNP)的可逆性能力(a)奈米銀粒子(AgNP)的溶液、膜及回溶溶液之光譜圖(b)奈米銀粒子(AgNP)溶液之穿透式電子顯微鏡(TEM)圖(c)奈米銀粒子(AgNP)回溶溶液之穿透式電子顯微鏡(TEM)圖[Ag-NSP(7/93)/PVA=10/90]；圖13顯示不同穩定劑奈米銀粒子/黏土(AgNP/clay)對大腸桿菌的抗菌測試結果(奈米銀粒子(AgNP)之濃度為10 ppm)；圖14顯示奈米銀粒子/奈米矽片(AgNP/NSP)之不同比例對革蘭性陰性菌及對革蘭氏陽性菌的抗菌能力(a) 大腸桿菌(銀濃度10ppm),(b)綠膿桿菌(銀濃度20ppm),(c)金黃色葡萄球菌(銀濃度30ppm),and(d)化膿性鏈球菌(銀濃度10ppm)，控制組為奈米矽片(NSP)；圖15為掃描式電子顯微鏡(FE-SEM)圖，顯示奈米銀粒子/奈米矽片(AgNP/NSP)與大腸桿菌培養後的型態(銀濃度10ppm)；圖16為掃描式電子顯微鏡(FE-SEM)圖，顯示奈米銀粒子/奈米矽片(AgNP/NSP)與金黃色葡萄球菌培養後的型態(銀濃度10ppm)；圖17顯示奈米銀粒子(AgNP)大小相近但不同重量比之奈米銀粒子/奈米矽片(AgNP/NSP)對大腸桿菌的抗菌能力，控制組為0.1wt%的奈米矽片(NSP)。Figure 1 is a schematic diagram showing the preparation of nanosheets and the stable formation of nano-silver particles; Figure 2 is an ultraviolet-visible spectrum showing nano-silver particles/nanosheets reduced by ethanol (AgNP/NSP, 7 /93) solution; Figure 3 is an ultraviolet-visible spectrum showing nano-silver particles/montmorillonite (AgNP/MMT, 7/93) solution reduced by ethanol; Figure 4 is an ultraviolet-visible spectrum showing methanol Reduced nano silver particles/nano bismuth tablets (AgNP/NSP, 7/93) solution; Figure 5 is an ultraviolet-visible spectroscopy chart showing nano silver particles/nano bismuth tablets (AgNP/ reduced with isopropanol) NSP, 7/93) solution; Figure 6 is a transmission electron microscope (TEM) image showing the difference in analyzed particle size distribution (a) nano silver particles / nano sputum tablets (AgNP / NSP) _ ethanol reduction (b ) Nano silver particles / montmorillonite (AgNP / MMT) _ ethanol reduction (c) nano silver particles / nano bismuth tablets (AgNP / NSP) _ methanol reduction (d) nano silver particles / nano sputum tablets ( AgNP/NSP)_Isopropanol reduction; Figure 7 is a transmission electron microscope (TEM) image showing changes in particle size before and after heat treatment (a) (d) Ag/SMA3000-M2070(b)(e)Ag/ MMT(c)(f)Ag/NSP.(a)~(c) before heating (d)~(f) After heating 8 H; Figure 8 is an ultraviolet-visible spectrum showing the change in absorption peak position after film formation and treatment (a) AgNP/Clay appearance (b) AgNP/NSP UV Analysis Figure (c) UV analysis of AgNP/MMT (black line is the solution before film formation; red line is film state; blue line is solution after remelting); Figure 9 is transmission electron microscope (TEM) , showing the average particle size of different weight ratios of nano silver particles/nano bismuth tablets (AgNP/NSP) (a) 0.5/99.5 (P3.6) (b) 1/99 (P3.8), (c 7/93 (P5), (d) 15/85 (P9), (e) 30/70 (P17) and (f) 50/50 (P35); Figure 10 is a transmission electron microscope (TEM) , showing the average particle size of silver particles in different weight ratios of ethanol/water (EtOH/H 2 O) (a) 1/1, (b) 3/1, (c) 5/1, (d) 10/ 1, (e) 1 / 0, in addition (f) is the comparison of the average particle size of different ethanol content; Figure 11 is the ultraviolet-visible spectrum, showing the reversibility of nano-silver particles (AgNP) at different particle sizes Capability (a) Photograph of film after formation of nano silver particles (AgNP) (b) Spectra of solution (c) Spectra of film (d) Spectrum of solution after re-dissolving; Figure 12 is an ultraviolet-visible spectrum Penetrating electron microscopy (TEM) diagram showing the reversibility of nano silver particles (AgNP) (a) spectrum of solution of nano silver particles (AgNP), film and solution of resolved solution (b) solution of nano silver particles (AgNP) Transmission electron microscope (TEM) image (c) Transmission electron microscopy (TEM) image of nano silver particle (AgNP) solution (Ag-NSP (7/93)/PVA=10/90]; 13 shows the antibacterial test results of different stabilizer nano silver particles/clay (AgNP/clay) against Escherichia coli (concentration of nano silver particles (AgNP) is 10 ppm); Figure 14 shows nano silver particles/nano wafers Antibacterial ability of different ratios of (AgNP/NSP) to Gram-negative bacteria and Gram-positive bacteria (a) Escherichia coli (silver concentration 10 ppm), (b) Pseudomonas aeruginosa (silver concentration 20 ppm), (c) Staphylococcus aureus (silver concentration 30ppm), and (d) S. pyogenes (silver concentration 10ppm), control group is nano-slices (NSP); Figure 15 is a scanning electron microscope (FE-SEM) diagram, showing Nano silver particles/nano bismuth tablets (AgNP/NSP) and the morphology of E. coli culture (silver concentration 10ppm); Figure 16 is a scanning electron microscope (FE-SEM) image showing nano silver particles/nano Bracts (AgNP/NSP) and cultured with Staphylococcus aureus State (silver concentration 10ppm); Figure 17 shows the nano-silver particles (AgNP) of similar size but different weight ratio of nano-silver particles / nano-slices (AgNP / NSP) antibacterial ability to E. coli, control group is 0.1wt % of nano-slices (NSP).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005060831A (en) * | 2003-07-29 | 2005-03-10 | Mitsubishi Materials Corp | Composite metal powder and its production method, and silver clay |
| TWI243836B (en) * | 2000-06-01 | 2005-11-21 | Eternal Chemical Co Ltd | Syndiotactic polystyrene/clay nanocomposite material and its manufacturing method |
| TW200924840A (en) * | 2007-12-07 | 2009-06-16 | Univ Nat Taiwan | Steady dispersion nano metal/inorganic clay composite and its manufacture method |
| TW201113399A (en) * | 2009-10-02 | 2011-04-16 | Univ Nat Chunghsing | Manufacturing method of nano-sized metal particle |
| TW201215415A (en) * | 2010-10-15 | 2012-04-16 | Univ Nat Taiwan | A composite of spherical silver nanoparticles and layered inorganic clay |
| TW201226048A (en) * | 2010-12-29 | 2012-07-01 | Univ Nat Taiwan | Method for dispersing metallic nanoparticle and composite thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI243836B (en) * | 2000-06-01 | 2005-11-21 | Eternal Chemical Co Ltd | Syndiotactic polystyrene/clay nanocomposite material and its manufacturing method |
| JP2005060831A (en) * | 2003-07-29 | 2005-03-10 | Mitsubishi Materials Corp | Composite metal powder and its production method, and silver clay |
| TW200924840A (en) * | 2007-12-07 | 2009-06-16 | Univ Nat Taiwan | Steady dispersion nano metal/inorganic clay composite and its manufacture method |
| TW201113399A (en) * | 2009-10-02 | 2011-04-16 | Univ Nat Chunghsing | Manufacturing method of nano-sized metal particle |
| TW201215415A (en) * | 2010-10-15 | 2012-04-16 | Univ Nat Taiwan | A composite of spherical silver nanoparticles and layered inorganic clay |
| TW201226048A (en) * | 2010-12-29 | 2012-07-01 | Univ Nat Taiwan | Method for dispersing metallic nanoparticle and composite thereof |
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