TWI496615B - Method for prepareing silver particles and core-shell silver particles - Google Patents
Method for prepareing silver particles and core-shell silver particles Download PDFInfo
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- TWI496615B TWI496615B TW102123840A TW102123840A TWI496615B TW I496615 B TWI496615 B TW I496615B TW 102123840 A TW102123840 A TW 102123840A TW 102123840 A TW102123840 A TW 102123840A TW I496615 B TWI496615 B TW I496615B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
Description
本發明是有關於一種銀顆粒的製造方法，特別是有關於一種中空及核殼結構銀顆粒的製造方法；及一種核殼結構銀顆粒。The present invention relates to a method for producing silver particles, and more particularly to a method for producing hollow and core-shell structured silver particles; and a core-shell structured silver particle.
近年來核殼及中空結構銀顆粒因為其優異的性質且能被廣泛用於導體、構裝及敷材而逐漸被重視，像是抗菌敷料，銀導電膠等都是銀顆粒目前在市面上流通的應用。但目前生成銀顆粒的主要方法為還原法(reduction)與溶膠凝膠法(sol-gel)為主，皆為批次的化學方法，以商業量產的角度看來，較不具量產潛力。In recent years, core-shell and hollow-structured silver particles have been gradually recognized for their excellent properties and can be widely used in conductors, structures and materials. For example, antibacterial dressings, silver conductive adhesives, etc. are all currently circulating in the market. Applications. However, the current main methods for producing silver particles are reduction and sol-gel, which are batch chemical methods. From the perspective of commercial mass production, they have less potential for mass production.
銀顆粒在目前的應用上，大多使用實心銀顆粒，但實心銀顆粒的性質也有能改進的部分，例如抗菌敷料在使用期限到達時，實心銀顆粒還沒被消耗完，造成材料的浪費；或是導電銀膠中的實心銀顆粒與載體密度差別過大，會因長時間久置而沉降造成膠體不均勻，影響材料性質。In the current application, silver particles mostly use solid silver particles, but the properties of solid silver particles can also be improved. For example, when the antibacterial dressing reaches the service life, the solid silver particles are not consumed, resulting in waste of materials; It is the difference between the density of the solid silver particles in the conductive silver paste and the carrier, which may cause the colloid to be uneven due to the long time standing, which affects the material properties.
銀顆粒中空製備的機制目前以硬模板、軟模板及克肯達爾效應(Kirkendall effect)為主。但硬模板具有需酸鹼去除模板而易造成環境汙染及酸鹼處理的問題。而軟模板 有需額外升溫去除高分子模板及留下殘餘碳汙染的可能。克肯達爾效應則有程序複雜及高設備成本的缺點。The mechanism of hollow preparation of silver particles is currently dominated by hard template, soft template and Kirkendall effect. However, the hard template has the problem of requiring acid and alkali to remove the template and easily causing environmental pollution and acid and alkali treatment. Soft template There is a need to increase the temperature of the polymer template and leave residual carbon contamination. The Kekendal effect has the disadvantages of complicated procedures and high equipment costs.
因此，本發明的目的在於提供一種連續式製備中空及核殼銀顆粒的方法，其不但可以量產銀顆粒供業界使用，並選擇以甘胺酸(Glycine ritrate)法作為孔洞形成機制。由於甘胺酸為低分子量易於升溫時所去除，故更可改善先前技術之缺點，所生產之中空及核殼銀顆粒更能替代目前使用之實心銀顆粒以增進使用效能。Accordingly, it is an object of the present invention to provide a method for continuously preparing hollow and core-shell silver particles which can be used for mass production of silver particles for use in the industry, and a Glycine ritrate method as a pore formation mechanism. Since the glycine acid is removed when the low molecular weight is easy to be heated, the disadvantages of the prior art can be further improved, and the hollow and core-shell silver particles produced can replace the solid silver particles currently used to improve the use efficiency.
本發明之一態樣提供一種製備核殼及中空銀顆粒的方法，其包含下列步驟。混合銀無機鹽及甘胺酸或澱粉於極性溶劑中以製備前驅物溶液，其中此銀無機鹽/銀無機鹽加上甘胺酸或澱粉之莫耳百分比為5~50mol%，且此銀無機鹽與甘胺酸或澱粉佔該前驅物溶液的0.01~10wt%。霧化此前驅物溶液，形成前驅物液滴。以及加熱此前驅物液滴，使此前驅物液滴裂解並製備出銀顆粒。所製備之銀顆粒具有核殼或中空結構。One aspect of the present invention provides a method of preparing a core shell and hollow silver particles comprising the following steps. Mixing a silver inorganic salt and a glycine acid or a starch in a polar solvent to prepare a precursor solution, wherein the silver inorganic salt/silver inorganic salt plus a glycine acid or starch has a molar percentage of 5 to 50 mol%, and the silver inorganic The salt and the glycine acid or starch account for 0.01 to 10% by weight of the precursor solution. The precursor solution is atomized to form precursor droplets. And heating the precursor droplets to cleave the precursor droplets and prepare silver particles. The prepared silver particles have a core shell or a hollow structure.
根據本發明一實施方式，銀無機鹽係硝酸銀或醋酸銀。According to an embodiment of the invention, the silver inorganic salt is silver nitrate or silver acetate.
根據本發明一實施方式，極性溶劑係水。According to an embodiment of the invention, the polar solvent is water.
根據本發明一實施方式，銀無機鹽與甘胺酸或澱粉佔前驅物溶液的1wt%。According to an embodiment of the invention, the silver inorganic salt and the glycine acid or starch comprise 1% by weight of the precursor solution.
根據本發明一實施方式，銀無機鹽/銀無機鹽加上甘胺酸之莫耳百分比介於12.5~50mol%時，製備出之銀顆 粒為核殼結構。According to an embodiment of the present invention, the silver inorganic salt/silver inorganic salt plus the molar percentage of glycine is between 12.5 and 50 mol%, and the silver particles are prepared. The granules are core-shell structures.
根據本發明一實施方式，銀無機鹽/銀無機鹽加上甘胺酸之莫耳百分比為小於12.5mol%時，製備出之銀顆粒為空心結構。According to an embodiment of the present invention, when the silver inorganic salt/silver inorganic salt plus the molar percentage of glycine is less than 12.5 mol%, the prepared silver particles have a hollow structure.
根據本發明一實施方式，加熱步驟包含。溶劑蒸發。溶質過飽和析出。熱裂解。以及氧化反應。According to an embodiment of the invention, the heating step comprises. The solvent evaporates. The solute is supersaturated and precipitated. Thermal cracking. And oxidation reaction.
本發明之另一態樣提供一種核殼結構銀顆粒，係由上述方法製造而得。Another aspect of the present invention provides a core-shell structured silver particle obtained by the above method.
根據本發明一實施方式，此核殼結構銀顆粒含有一銀核心，一中空層位於銀核心之外層，以及一銀殼層包覆中空層。According to an embodiment of the invention, the core-shell structure silver particles comprise a silver core, a hollow layer is located outside the silver core layer, and a silver shell layer covers the hollow layer.
根據本發明一實施方式，此核殼結構銀顆粒之粒徑大小為約100至1000奈米。According to an embodiment of the present invention, the core-shell structure silver particles have a particle size of about 100 to 1000 nm.
100、110、120‧‧‧步驟100, 110, 120‧ ‧ steps
210‧‧‧前驅物溶液210‧‧‧Precursor solution
220‧‧‧超音波加濕機220‧‧‧Ultrasonic humidifier
230‧‧‧石英管230‧‧‧Quartz tube
240‧‧‧管狀爐240‧‧‧Tubular furnace
250‧‧‧不鏽鋼管集塵器250‧‧‧Stainless steel pipe dust collector
260‧‧‧高壓放電設備260‧‧‧High-voltage discharge equipment
270‧‧‧冷卻水270‧‧‧ cooling water
280‧‧‧濾紙280‧‧‧ filter paper
290‧‧‧抽氣幫浦290‧‧‧Exhaust pump
710‧‧‧銀核心710‧‧‧Silver core
720‧‧‧中空層720‧‧‧ hollow layer
730‧‧‧銀殼層730‧‧‧Silver shell
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之詳細說明如下：第1圖繪示本發明之一實施例的一種製備核殼及中空銀顆粒的方法的流程圖。The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Flow chart of the method of granules.
第2圖繪示本發明之一實施例的一種製備核殼及中空銀顆粒的方法的一製程裝置示意圖。2 is a schematic view of a process apparatus for preparing a core shell and hollow silver particles according to an embodiment of the present invention.
第3A-3B圖係本發明之一實施例的硝酸銀與甘胺酸經熱重分析所得之熱分解行為圖。3A-3B is a graph showing the thermal decomposition behavior of silver nitrate and glycine by thermogravimetric analysis in an embodiment of the present invention.
第4A-4D圖係本發明比較例1及實驗例1-3所製備之 銀顆粒TEM圖。4A-4D are prepared in Comparative Example 1 and Experimental Examples 1-3 of the present invention. TEM image of silver particles.
第5A-5C圖係本發明比較例2及實驗例4-5所製備之銀顆粒TEM圖。5A-5C are TEM images of silver particles prepared in Comparative Example 2 and Experimental Example 4-5 of the present invention.
第6圖係本發明實驗例6所製備之銀顆粒TEM圖。Fig. 6 is a TEM image of silver particles prepared in Experimental Example 6 of the present invention.
第7圖繪示本發明之一實施例的一種核殼結構銀顆粒的剖面示意圖。FIG. 7 is a schematic cross-sectional view showing a core-shell structure silver particle according to an embodiment of the present invention.
以下將以圖式揭露本發明之複數個實施方式，為明確說明起見，許多實務上的細節將在以下敘述中一併說明。然而，應瞭解到，這些實務上的細節不應用以限制本發明。也就是說，在本發明部分實施方式中，這些實務上的細節是非必要的。此外，為簡化圖式起見，一些習知慣用的結構與元件在圖式中將以簡單示意的方式顯示之。The embodiments of the present invention are disclosed in the following drawings, and the details of However, it should be understood that these practical details are not intended to limit the invention. That is, in some embodiments of the invention, these practical details are not necessary. In addition, some of the conventional structures and elements are shown in the drawings in a simplified manner in the drawings.
本發明之一態樣提供一種製備核殼及中空銀顆粒的方法，其包含下列步驟，請參照第1圖。首先步驟100為，混合銀無機鹽及甘胺酸或澱粉於極性溶劑中以製備前驅物溶液，其中此銀無機鹽/銀無機鹽加上甘胺酸或澱粉之莫耳百分比為5~50mol%，且此銀無機鹽與甘胺酸或澱粉佔該前驅物溶液的0.01~10wt%。在一實施例中，銀無機鹽為硝酸鹽或醋酸鹽。在另一實施例中，極性溶劑為水。在一實施例中，銀無機鹽/銀無機鹽加上甘胺酸之莫耳百分比為約12.5~50mol%時，會製備出核殼結構銀顆粒。在另一實施例中銀無機鹽/甘胺酸之莫耳百分比小於12.5mol%時，會 製備出中空結構銀顆粒。在另一實施例中銀無機鹽/銀無機鹽加上澱粉之莫耳百分比為50mol%時，會製備出中空結構銀顆粒。One aspect of the present invention provides a method of preparing a core shell and hollow silver particles, comprising the following steps, please refer to FIG. First, in step 100, a silver inorganic salt and a glycine acid or a starch are mixed in a polar solvent to prepare a precursor solution, wherein the silver inorganic salt/silver inorganic salt plus the percentage of the molar content of the glycine acid or the starch is 5 to 50 mol%. And the silver inorganic salt and the glycine acid or starch account for 0.01 to 10% by weight of the precursor solution. In one embodiment, the silver inorganic salt is a nitrate or acetate. In another embodiment, the polar solvent is water. In one embodiment, when the silver inorganic salt/silver inorganic salt plus the molar percentage of glycine is about 12.5 to 50 mol%, core-shell structured silver particles are prepared. In another embodiment, when the percentage of silver inorganic salt/glycine is less than 12.5 mol%, Hollow structured silver particles were prepared. In another embodiment, when the silver inorganic salt/silver inorganic salt plus the molar percentage of the starch is 50 mol%, hollow structure silver particles are prepared.
步驟110為將前驅物溶液霧化，使其均勻分散成前驅物液滴，在本發明之一實施例中，使用超音波加濕機來霧化前驅物溶液，當溶劑為水時，超音波頻率為1.65MHz。在本發明之一實施例中，前驅物液滴大小為約3至20微米，液滴大小與前驅物濃度成正相關。此銀無機鹽與甘胺酸佔前驅物溶液約0.01至10wt%，為較佳霧化之濃度範圍。Step 110 is to atomize the precursor solution to uniformly disperse into droplets of the precursor. In an embodiment of the invention, the ultrasonic humidifier is used to atomize the precursor solution, and when the solvent is water, the ultrasonic wave The frequency is 1.65 MHz. In one embodiment of the invention, the precursor droplet size is from about 3 to 20 microns and the droplet size is positively correlated with the precursor concentration. The silver inorganic salt and glycine account for about 0.01 to 10% by weight of the precursor solution, which is a preferred atomization concentration range.
接下來步驟120為將此前驅物液滴加熱，加熱至前驅物液滴裂解而製備出銀顆粒，而前驅物的其他部分皆被熱解為氣體。在本發明之一實施例中，加熱裝置為控溫管形加熱爐(管狀爐)，可將管內溫度調控為三區段，預熱段(200~400℃)、鍛燒段(500~800℃)，以及降溫段(300~500℃)。在本發明之另一實施例中，此加熱步驟包含溶劑蒸發、溶質過飽和析出、熱裂解，及氧化反應。Next step 120 is to prepare the silver particles by heating the precursor droplets, heating to the precursor droplets, and the other portions of the precursor are pyrolyzed into gases. In an embodiment of the invention, the heating device is a temperature-controlled tubular heating furnace (tubular furnace), and the temperature in the tube can be controlled into three sections, a preheating section (200-400 ° C), and a calcining section (500~). 800 ° C), and cooling section (300 ~ 500 ° C). In another embodiment of the invention, the heating step comprises solvent evaporation, solute supersaturation, thermal cracking, and oxidation.
第2圖繪示本發明之一實施例之具體裝置組合，但本發明方法並不限定於只以此裝置實施。如圖所示，混合好之前驅物溶液210加至超音波震盪器220中，被霧化形成前驅物液滴，前驅物液滴送入石英管230中進入管狀爐240，在管狀爐240中，前驅物液滴被裂解並氧化而製備出銀顆粒，在此實施例中以由不鏽鋼管集塵器250加上高壓放電設備260組成的靜電集塵器蒐集銀顆粒，在管狀爐熱解後之氣體經過冷卻水270及濾紙280由抽氣幫浦290排 出。Fig. 2 is a view showing a specific device combination of an embodiment of the present invention, but the method of the present invention is not limited to being implemented only by this device. As shown, the mixed precursor solution 210 is added to the ultrasonic oscillator 220, atomized to form precursor droplets, and the precursor droplets are fed into the quartz tube 230 into the tubular furnace 240, in the tubular furnace 240. The precursor droplets are cleaved and oxidized to prepare silver particles. In this embodiment, silver particles are collected by an electrostatic precipitator composed of a stainless steel tube dust collector 250 plus a high voltage discharge device 260, after pyrolysis of the tubular furnace. The gas passes through the cooling water 270 and the filter paper 280 is exhausted by the pump 290 Out.
第3A圖與第3B圖係本發明之一實施例之硝酸銀與甘胺酸經熱重分析所得之熱分解行為圖，由第3A圖可知硝酸銀有兩個熱分解階段，第一階段由室溫升高至442℃且重量下降5%，理論推估此時硝酸銀裂解為亞硝酸銀，第二階段當溫度由442℃上升至700℃時，試片重量由95%降至67%，故推測此階段被熱分解到至剩下銀。由第3B圖可知甘胺酸有兩個熱分解階段，第一階段由室溫升高至260℃時重量下降51%，第二階段當溫度由上升至650℃以上時，甘氨酸會完全裂解，無重量殘留。並由此決定在進行裂解步驟時的溫度需至少為700℃。3A and 3B are diagrams showing the thermal decomposition behavior of silver nitrate and glycine by thermogravimetric analysis according to an embodiment of the present invention. It can be seen from Fig. 3A that silver nitrate has two thermal decomposition stages, and the first stage is from room temperature. Increased to 442 ° C and the weight decreased by 5%, theoretically estimated that silver nitrate was cracked into silver nitrite at this time, the second stage when the temperature rose from 442 ° C to 700 ° C, the test piece weight decreased from 95% to 67%, it is speculated This stage is thermally decomposed to the remaining silver. It can be seen from Fig. 3B that glycine has two thermal decomposition stages. The first stage increases the weight from room temperature to 260 ° C by 51%. In the second stage, when the temperature rises above 650 ° C, glycine is completely cleaved. No weight residue. It is thus determined that the temperature at which the cracking step is carried out needs to be at least 700 °C.
以下列舉數個實施例以更詳盡闡述本發明之方法，然其僅為例示說明之用，並非用以限定本發明，本發明之保護範圍當以後附之申請專利範圍所界定者為準。The following examples are given to illustrate the method of the present invention in more detail, and are intended to be illustrative only and not to limit the invention, and the scope of the invention is defined by the scope of the appended claims.
實施例Example
A.以不同比率之硝酸銀與甘胺酸製備之前驅物溶液製備銀顆粒。A. Silver particles were prepared by preparing a precursor solution with different ratios of silver nitrate and glycine.
比較例1；前驅物溶液中無甘胺酸Comparative Example 1; no glycine in the precursor solution
製備1wt%之硝酸銀水溶液為前驅物溶液，實驗裝置如第2圖所繪示，將混合好之前驅物溶液210加至超音波震盪器220中，被霧化形成前驅物液滴，前驅物液滴送入石英管230中進入管狀爐240，在管狀爐240中經過了預熱段(200~400℃)、鍛燒段(500~800℃)，以及降溫段 (300~500℃)，並經歷了溶劑蒸發、溶質過飽和析出、熱裂解，及氧化反應後，前驅物液滴被裂解而製備出銀顆粒，在此實施例中以由不鏽鋼管集塵器250加上高壓放電設備260組成的靜電集塵器蒐集銀顆粒，在管狀爐內氧化後之氣體經過冷卻水270及濾紙280由抽氣幫浦290排出。A 1 wt% silver nitrate aqueous solution is prepared as a precursor solution, and the experimental apparatus is as shown in FIG. 2, and the mixed precursor solution 210 is added to the ultrasonic oscillator 220, which is atomized to form a precursor droplet, and the precursor liquid. Dropping into quartz tube 230 into tubular furnace 240, passing through preheating section (200~400 °C), calcining section (500~800 °C), and cooling section in tubular furnace 240 (300~500 ° C), and after undergoing solvent evaporation, solute supersaturation precipitation, thermal cracking, and oxidation reaction, the precursor droplets are cracked to prepare silver particles, in this embodiment by a stainless steel tube dust collector 250 An electrostatic precipitator composed of a high-voltage discharge device 260 collects silver particles, and the gas oxidized in the tubular furnace is discharged from the pumping pump 290 through the cooling water 270 and the filter paper 280.
第4A圖為此比較例1之銀顆粒產物的TEM圖，圖中顯示深色部分表示實心顆粒。顆粒直徑約360至1120奈米。Fig. 4A is a TEM image of the silver particle product of Comparative Example 1, in which the dark portion indicates solid particles. The particles have a diameter of about 360 to 1120 nm.
實驗例1；前驅物溶液中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為25mol%Experimental Example 1; the percentage of moles of silver nitrate/silver nitrate plus glycine in the precursor solution was 25 mol%
製備1wt%之前驅物溶液，其中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為25mol%。實驗製程同比較例1。A 1 wt% precursor solution was prepared in which the percentage of moles of silver nitrate/silver nitrate plus glycine was 25 mol%. The experimental procedure was the same as in Comparative Example 1.
第4B圖係實驗例1所製備之銀顆粒之TEM圖，由圖中可觀察到深色的核心、殼層，以及淺色的中空部分形成之核殼結構，顆粒直徑約118至216奈米，孔隙率為22.6%。Figure 4B is a TEM image of the silver particles prepared in Experimental Example 1, from which a dark core, a shell layer, and a light-colored hollow portion are formed, and the particle diameter is about 118 to 216 nm. The porosity is 22.6%.
實驗例2；前驅物溶液中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為14.2mol%Experimental Example 2; the percentage of moles of silver nitrate/silver nitrate plus glycine in the precursor solution was 14.2 mol%.
製備1wt%之前驅物溶液，其中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為14.2mol%。實驗製程同比較例1。A 1 wt% precursor solution was prepared in which the percentage of moles of silver nitrate/silver nitrate plus glycine was 14.2 mol%. The experimental procedure was the same as in Comparative Example 1.
第4C圖係實驗例2所製備之銀顆粒之TEM圖，由圖中可觀察到深色的核心、殼層，以及淺色的中空部分形成之核殼結構，顆粒直徑約127至195奈米，孔隙率為27.2%。Figure 4C is a TEM image of the silver particles prepared in Experimental Example 2, from which a dark core, a shell layer, and a light-colored hollow portion are formed, and the particle diameter is about 127 to 195 nm. The porosity was 27.2%.
實驗例3；前驅物溶液中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為12.5mol%Experimental Example 3; the percentage of moles of silver nitrate/silver nitrate plus glycine in the precursor solution was 12.5 mol%
製備1wt%之前驅物溶液，其中硝酸銀/硝酸銀加上甘胺酸之莫耳百分比為12.5mol%。實驗製程同比較例1。A 1 wt% precursor solution was prepared in which the percentage of moles of silver nitrate/silver nitrate plus glycine was 12.5 mol%. The experimental procedure was the same as in Comparative Example 1.
第4D圖係實驗例3所製備之銀顆粒之TEM圖，由圖中可觀察到深色的殼層，以及淺色的中空部分形成之中空結構，顆粒直徑約143至235奈米，孔隙率為36.5%。4D is a TEM image of the silver particles prepared in Experimental Example 3, in which a dark shell layer and a hollow structure formed by a hollow hollow portion are observed, and the particle diameter is about 143 to 235 nm, and the porosity is It is 36.5%.
B.以不同比率醋酸銀與甘胺酸製備之前驅物溶液製備銀顆粒。B. Silver particles were prepared by preparing a precursor solution with different ratios of silver acetate and glycine.
比較例2；前驅物溶液中無甘胺酸Comparative Example 2; no glycine in the precursor solution
實驗製程如同比較例1，差別在於將前驅物溶液改為1wt%之醋酸銀。The experimental procedure was the same as in Comparative Example 1, except that the precursor solution was changed to 1 wt% of silver acetate.
第5A圖為比較例2所製備之銀顆粒之TEM圖，由圖中可知所製備之銀顆粒為實心顆粒。Fig. 5A is a TEM image of the silver particles prepared in Comparative Example 2, from which it is understood that the prepared silver particles are solid particles.
實驗例4；前驅物溶液中醋酸銀/醋酸銀加上甘胺酸之莫耳百分比為25mol%Experimental Example 4; the percentage of moles of silver acetate/silver acetate plus glycine in the precursor solution was 25 mol%
實驗製程如同比較例1，前驅物溶液改為1wt%之醋酸銀與甘胺酸之混和溶液，其中醋酸銀/醋酸銀加上甘胺酸之莫耳百分比為25mol%。The experimental procedure was the same as in Comparative Example 1, and the precursor solution was changed to a mixed solution of 1 wt% of silver acetate and glycine, wherein the percentage of moles of silver acetate/silver acetate plus glycine was 25 mol%.
第5B圖為實驗例4所製備之銀顆粒之TEM圖，由圖中可知所製備之銀顆粒具有深色的核心以及淺色的核殼結構，孔隙率為26.99%。Fig. 5B is a TEM image of the silver particles prepared in Experimental Example 4. It can be seen from the figure that the prepared silver particles have a dark core and a light-colored core-shell structure, and the porosity is 26.99%.
實驗例5；前驅物溶液中醋酸銀/醋酸銀加上甘胺酸Experimental Example 5; silver acetate/silver acetate plus glycine in the precursor solution 之莫耳百分比為16.7mol%The percentage of moles is 16.7 mol%
實驗製程如同比較例1，前驅物溶液改為1wt%之醋酸銀與甘胺酸之混和溶液，其中醋酸銀/醋酸銀加上甘胺酸之莫耳百分比為16.7mol%。The experimental procedure was the same as in Comparative Example 1, and the precursor solution was changed to a mixed solution of 1 wt% of silver acetate and glycine, wherein the percentage of moles of silver acetate/silver acetate plus glycine was 16.7 mol%.
第5C圖為實驗例5所製備之銀顆粒之TEM圖，由圖中可知所製備之銀顆粒具有深色的核心以及淺色的核殼結構，孔隙率為33.81%。Fig. 5C is a TEM image of the silver particles prepared in Experimental Example 5. It can be seen from the figure that the prepared silver particles have a dark core and a light-colored core-shell structure, and the porosity is 33.81%.
C以硝酸銀與澱粉製備之前驅物溶液製備銀顆粒。C Silver particles were prepared by preparing a precursor solution from silver nitrate and starch.
實驗例6；前驅物溶液中硝酸銀/硝酸銀加上澱粉之莫耳百分比為50mol%。Experimental Example 6; the percentage of moles of silver nitrate/silver nitrate plus starch in the precursor solution was 50 mol%.
實驗製程如同比較例1，前驅物溶液改為50mol%之硝酸銀與澱粉之混和溶液，其中硝酸銀/硝酸銀加上澱粉之莫耳百分比為50mol%。The experimental procedure was the same as in Comparative Example 1, and the precursor solution was changed to a mixed solution of 50 mol% of silver nitrate and starch, wherein the percentage of moles of silver nitrate/silver nitrate plus starch was 50 mol%.
第6圖為實驗例6所製備之銀顆粒之TEM圖，由圖中可知所製備之銀顆粒為一由深色的殼層，以及淺色的中空部分形成之中空結構。Fig. 6 is a TEM image of the silver particles prepared in Experimental Example 6. It is understood that the prepared silver particles are a hollow structure formed of a dark shell layer and a light colored hollow portion.
由所列舉之實施例中可知，以本發明之添加甘胺酸或澱粉於前驅物溶液中之方法可以連續製備核殼或中空銀顆粒。與比較例相較，實驗例中添加甘胺酸或澱粉於銀無機鹽前驅物溶液中後，最後便可製備出核殼或中空結構的銀顆粒，而比較例中只能製備實心之銀顆粒，而且尺寸也大於中空與核殼之銀顆粒。As is apparent from the examples exemplified, the core shell or hollow silver particles can be continuously produced by the method of adding glycine acid or starch in the precursor solution of the present invention. Compared with the comparative example, after adding glycine acid or starch to the silver inorganic salt precursor solution in the experimental example, silver particles of a core shell or a hollow structure can be finally prepared, and in the comparative example, only solid silver particles can be prepared. And the size is also larger than the silver particles of the hollow and core shell.
第7圖繪示本發明之一實施方式製備之銀顆粒示 意圖。包含一個銀核心710，一個位於銀核心710外之中空層720，以及包覆著中空層720之銀殼層730。Figure 7 is a diagram showing the silver particles prepared by an embodiment of the present invention. intention. A silver core 710, a hollow layer 720 outside the silver core 710, and a silver shell layer 730 covering the hollow layer 720 are included.
本發明所提供之可連續製備核殼及空心結構銀顆粒的方法，除了是一連續性製程可應用於工業量產之外，其可調控孔隙度的特性也可應用於現今市售使用銀顆粒的產品上，可節省銀的用量及成本，也可以依產品使用的時間長短來控制銀顆粒的中空程度，使銀的使用率提升到最高。The method for continuously preparing core shell and hollow structure silver particles provided by the invention can be applied to industrial mass production in addition to being a continuous process, and the properties of the controllable porosity can also be applied to commercially available silver particles. In the product, the amount and cost of silver can be saved, and the degree of hollowness of the silver particles can be controlled according to the length of time used for the product, so that the utilization rate of silver is maximized.
例如抗菌敷料上的實心銀顆粒常因使用期限到了需丟棄，但顆粒內部仍有銀未反應，故本發明之可調控空孔比例的銀顆粒便可以依使用期限來調整所需銀顆粒之厚度，以減少材料浪費。For example, the solid silver particles on the antibacterial dressing often need to be discarded due to the use period, but there is still silver unreacted inside the particles, so the silver particles of the adjustable pore ratio of the present invention can adjust the thickness of the desired silver particles according to the use period. To reduce material waste.
銀導電膠中，因銀粉與有機載體密度差異過大，銀顆粒容易因為保存時間的關係而沉降，造成膠體密度不均，進而影響材料性質，中空銀粉則因內部為空氣，故可以大幅降低銀顆粒密度，減少內部密度差，進而大幅降低沉降現象。In the silver conductive adhesive, because the density difference between the silver powder and the organic carrier is too large, the silver particles are easily settled due to the preservation time, resulting in uneven colloid density, which in turn affects the material properties. The hollow silver powder is internally reduced to air, so the silver particles can be greatly reduced. Density, which reduces the difference in internal density, and thus greatly reduces the sedimentation phenomenon.
雖然本發明已以一較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
100、110、120‧‧‧步驟100, 110, 120‧ ‧ steps
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