1234789 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種非磁性鎳粉及其製作方法。 【先前技術】 鎳(nickel)為過渡金屬(transition metal)，隸屬於週期表中第八 族(group)第四週期(peri〇d)之鐵族，並為高熔點與極佳延展性的社 晶物質。 鎳粉是一種顆粒狀的金屬鎳材，可做為例如電子裝置(例如積 層陶瓷電容器(multilayer ceramic capacitors，MLCCs；))中的内部電 極之材料、磁性材料、電接觸材料(electrical c〇ntact material)、導 電膠材料(conductive adhesive material)、或催化劑(cataiySt)之用。 已知鎳為一種典型之鐵磁性(ferromagnetic)物質。鐵磁性物質 係指在具有外加磁場的條件下，物質會有強烈且持續的磁化作 用，甚至當外加磁場被移除時，磁化作用仍然存在。 當一個尚未經磁化的鐵磁性物質曝露於一個逐漸增強的磁場 中時，首先會緩慢的產生磁化作用，此即為所謂的初始磁化作用 (initial magnetization)。隨後，磁化作用的速率會加快，並會發生 1234789 飽和現象(saturation)。而若在飽和現象時，減少外加磁場的強度， 則磁化作用會減弱。然而，磁化作用的減弱過程與磁化作用的增 強過程並不相同。此外，當外加磁場減弱為零時，磁化作用並不 會消失，此即為所謂的剩磁現象(residualmagnetization)。而若將外 加磁場的方向反相(reverse)，並增加反相磁場的強度，則磁化作用 會為停止並且磁化作用的方向會被反相。之後，反向的磁化作用 逐漸成為飽和狀態。此時，即使外加磁場的強度為零，磁化作用 也不為零並且反向殘餘的磁化作用存在，因此產生不通過原點的 封閉曲線。此封閉曲線即稱為磁化曲線(magnetization curve)。磁化 曲線與磁區結構(magnetic domain structure)有著非常密切的關係。 一般而言’磁矩(magnetic moment)係為引起磁化作用的因素 之一’其係由平行的電子自旋(spin)導致，而且通常鐵磁性物質具 有較大的磁矩。此外，一般認為鐵磁性物質具有磁區，磁區為平 行的自旋團(clusters of parallel spins)。當施加磁場時，磁區會依磁 場的方向排列。即使當磁場移除時，磁區的方向仍會有一段長時 間維持不變，而產生殘餘磁化(resi(luai magnetization)。就這一點而 吕，當鐵磁性物質的溫度上升時，鐵磁性物質中電子自旋的排列 因熱運動而無秩序。因此，鐵磁性物質會失去鐵磁性並轉換為順 磁性（paramagnetic)物質。此溫度稱為居禮溫度（Curie temperature)。而讓磁通密度降到零所需要的反相磁場大小，即稱 為矯頑磁力(coercive force)。 1234789 鎳塊(bulk nickel)之磁性質如下：居里溫度約為353。〇，飽和 磁化(saturation magnetization)約為 0.617 τ，殘餘磁化約為 〇3〇〇 Τ，而矯頑磁力之大小約為239 A/m。 目前為止，鎳的同素異形物(allotrope)可分為具有面心立方 (face-centered cubic，FCC)晶體結構的金屬鎳與六方最密堆積 (hexagonal close packed，HCP)晶體結構的金屬鎳。 幾乎一般的鎳粉均為面心立方晶體結構的鐵磁性物質。很少 有製備具有六方最密堆積晶體結構的鎳粉的報告。具有六方最密 堆積晶體結構的鎳粉早已被預測為亦是一種鐵磁性物質。 依據史東納理論(Stoner theory) , DA· Papaconstantopoulos 等 人預測六方隶密堆積晶體結構的鎳必定是一種鐵磁性物質(請參 閱 D.A· Papaconstantopoulos, J. L. Fry, Ν· E. Brener， “Ferromagnetism in hexagonal close packed elements”，Physical Review B，Vol· 39, No· 4, 1989· 2· 1，pp 2526-2528)。 如前所述，鎳粉最具代表性的應用係用以作為電子裝置中的 内部電極’然而習知的鐵磁性鎳粉卻有如下之缺點： 首先’當以印刷法形成鎳内部電極所使用之電極糊^paste)所含 之鎳粉呈現磁性時，鎳粉會因具有磁性而彼此相互吸引而形成類 似磁鐵(magnet)和磁塊(agglomerated)之構造，進而難以形成均勻的 電極糊。 其次，隨著行動通訊與電腦技術之發展，電子設備紛紛使用 1234789 ° 、見以而，磁性物質在此種高頻寬下卻具有高阻抗，而難 以應用於此等設備中。 此等問題可藉由使用非磁性錄粉而解決。 【發明内容】 因此，本發明提供一種製作非磁性鎳粉的方法。 依據本發明之-方面，本發明提供之製作非磁_粉的方法 包含有如下步驟··（a)加熱—觀合物，此齡物包含有一錄前驅 物化合物(nickel precursor comp〇und)與一多元醇(p〇⑽以將^ 驅物化合物還原為具有面心立方晶體結構之金屬錄粉；以及⑼加 熱步驟⑷所得之混合物，以將至少一部分之具有面心立方晶體結 構的錄粉轉換為具有六方最密堆積晶體結構之錄粉。 【實施方式】 本發明提供-種製造非磁性鎳粉之方法，包含有如下步驟··⑻ 加熱-種混合物，此混合物包含有—錄前驅物化合物與一多元 醇’以將此祕驅物化合_原為具有面心立方(FCQ日日日體結構之 金屬鎳粉；及(b)加熱步驟⑻所得之混合物，以將至少一部分之具 有面心立方晶體結構的錄粉轉換為具有六方最密堆積晶體結狀 1234789 鎳粉。 的鎳粉在卜/人研究發現，當—般為磁性物質之具有FCC相 體 盖〜中破加熱時，會由rcc晶體結構轉換為㈣ 、、、。構，且域轉換則之祕鱗雜。 ‘種自鎳前驅物化合物製備 倣觀察，本發赌知之製作方法，即，在 …U之乡鱗之存訂職雜魏合轉喊FCC鎳 二牛與加熱二多凡醇中的FCC錄粉以轉換為HCP ·粉結合成為一系 1驟而完成。簡言之，本發明提供-非磁性鎳粉之方法。 雖然，本發明並未說明藉由加熱使得多元醇中的錄粉轉變結 構的理^’、然而其極有可能是因為溶解在多轉中的金屬鎳會進 订再結晶或奴反應之故。即使未_相轉移之確實機制，本發 明之有效性當不受此影響。、 對於鎳前_化合物並無_關，只要是可被Μ醇還原 成金屬鎳之含錄化合物均可使用。舉例而言，錄前驅物化合物包 括有鎳氧化物_)或鎳师ickel salt)。鎳鹽之實例包括有硫酸 錄、硝酸鎳、氯化鎳、溴化錄、氟化鎳、醋酸錄、乙醯丙嶋㈤制 aCetylacetonate)、及氫氧化錄。此等鎳前驅物化合物可單獨使用或 組合使用。 夕元醇係做為浴劑，以洛解鎳前驅物化合物。多元醇亦做為 還原劑，以將鎳前驅物還原成為金屬鎳。多元醇係一種醇類化合 1234789 物’具有二或更多個羥基(hydr〇xyl gr〇up)。美國專利第4539〇4i 號中，有詳述將多元醇作為還原劑之用的實例。 舉例而言，多元醇可為一種二醇((1丨〇1)之脂肪族甘醇或脂肪族 甘醇聚酯(aliphatic glyeQi p()1yeste]r；)。 脂肪族甘醇的實例包括有以C2-C6作為主鏈的伸烷基甘醇 (alkylene glycols) ’ 例如乙二醇(ethane(ji〇i)、丙二醇^r〇panedi〇i)、 丁一醇(butanediol)、戊_醇(pentanediol)、及己二醇(hexanediol)， 與從伸烧基甘醇(alkylene glyc〇ls)衍生出來的聚烷基甘醇 (polyalkyleneglyC〇is)，例如聚乙二醇⑽加邮沈⑱外也）。 又，脂肪族甘醇之實例可另包含有二伸乙甘醇(diethylene glycol) 一伸乙甘醇(triethylene glyC〇l)與二伸丙甘醇(dipr〇pyiene glycol) 〇 多元醇亦可為丙三醇(glyCer〇l)，其係一種三元醇(tri〇1)。 然而，本發明之多元醇種類當不限於上述之多元醇，且上述 之多元醇可以單獨或合併使用。 值得注意的是，本發明之多元醇的較佳種類係為乙二醇、二 伸乙甘醇、三伸乙甘醇、四伸乙甘醇、丨，2-丙二醇丨，2)、 1，3-丙二醇φΓ〇ρ肪edi〇l_l，3)、二伸丙甘醇(dipr〇pyleneglyc〇1)、j头 丁一醇(butanediol_l，2)、1，3_ 丁二醇(butanediol-l，3)、1，4_丁二醇 (butanediol-l，4)、或 2,3-丁二醇（butanediol-2,3)。 混合物中多元醇的初始含量並無特別限制，可依據鎳前驅物 1234789 化合物的溶解度而定。例如，混合物可含有一特定量的多元醇， 使得最初的鎳前驅物化合物含量約在〇.〇1至〇.5莫耳(m〇le)的範 圍。 為促使鎳前驅物化合物還原成為金屬鎳，本發明之方法包括 加熱含有鎳前驅物化合物與多元醇之混合物。在此，「加熱」是指 將含有鎳前驅物化合物與多元醇之混合物之溫度升溫至超過室溫 之溫度，特別是指超過約20°C之溫度。 為了更能有效地促使_侧，加熱溫度更料至少約45 -般而言’當加熱溫度愈鱗，縣鱗會愈快。然而當超 過-特定溫度時，還原速率則不會再有任何增加。而且，也許會 導致反應物變壞。就此點而言，加熱溫度可為約伽。C或較低。 在本發明的步驟⑻中，混合物的組成會隨時間而有所變化。 -開始，混合物包含絲驅物化合物與多構。在獅驅物化合 物還原成為rcc__之過财，混合物會先同時包含有錄前 驅物化合物與FCC相的金顧粉。若使物氫氧化錄(触le hydr〇xlde)以外的錄前驅物化合鱗，部分錄前驅物化合物會 化成為氫減鎳’紐還减為雜。聽的髓驅物化合物可 f接遇原成為金粉，而不經過先轉化成騎氧化制步驟。 ^太在經過-特定時間後’實質上全部的鎳前驅物化合物均還 原成為金粉。至於加熱的時間長短，麻缺加熱的溫声。 12 1234789 熟知此技術領域的-般人士，可以輕易地知道加熱的時間，因此， 此加熱時間長短並非實施本發明的重要因素。 在進行完步驟⑻之加熱混合物之後’進行步驟⑼，將金屬鎳 粉由FCC相轉換為HO>相。在步驟⑼中，鱗已經歷過步驟⑻ 之混合物加熱。 在步驟(b)中，若加熱混合物的溫度過低，則鎳粉由面心立方 晶體結構轉換為六方最密堆積晶體結構之相轉移會受阻。若加熱 的溫度太高，則相轉移速率可能不再增加。且混合物中的多元醇籲 亦可能因為加熱而分解。因此，步驟(b)的加熱溫度可在約赋 至約38(TC之範圍。1234789 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a non-magnetic nickel powder and a manufacturing method thereof. [Previous technology] Nickel is a transition metal, belonging to the iron group of the fourth period (period) of the eighth group in the periodic table, and has a high melting point and excellent ductility. Crystalline substance. Nickel powder is a granular metallic nickel material that can be used as, for example, materials for internal electrodes, magnetic materials, and electrical contact materials in electronic devices (such as multilayer ceramic capacitors (MLCCs)). ), Conductive adhesive material (conductive adhesive material), or catalyst (cataiySt). Nickel is known as a typical ferromagnetic substance. Ferromagnetic substance means that under the condition of an external magnetic field, the substance will have a strong and continuous magnetization. Even when the external magnetic field is removed, the magnetization still exists. When a ferromagnetic substance that has not been magnetized is exposed to a gradually increasing magnetic field, it will first slowly generate magnetization, which is the so-called initial magnetization. Subsequently, the rate of magnetization will increase and 1234789 saturation will occur. If the intensity of the external magnetic field is reduced during the saturation phenomenon, the magnetization will be weakened. However, the process of weakening magnetization is not the same as the process of increasing magnetization. In addition, when the applied magnetic field weakens to zero, the magnetization does not disappear, which is the so-called residual magnetization. If the direction of the external magnetic field is reversed and the strength of the reverse magnetic field is increased, the magnetization will stop and the direction of the magnetization will be reversed. After that, the reverse magnetization gradually became saturated. At this time, even if the intensity of the applied magnetic field is zero, the magnetization is not zero and the reverse residual magnetization exists, so a closed curve is generated that does not pass through the origin. This closed curve is called a magnetization curve. The magnetization curve is closely related to the magnetic domain structure. In general, 'magnetic moment is one of the factors causing magnetization', which is caused by parallel electron spins, and usually ferromagnetic substances have a large magnetic moment. In addition, it is generally considered that a ferromagnetic substance has a magnetic region, and the magnetic region is clusters of parallel spins. When a magnetic field is applied, the magnetic fields are aligned in the direction of the magnetic field. Even when the magnetic field is removed, the direction of the magnetic field will remain unchanged for a long period of time, resulting in resi (luai magnetization). At this point, when the temperature of the ferromagnetic substance rises, the ferromagnetic substance The arrangement of electron spins is disordered by thermal movement. Therefore, ferromagnetic substances lose ferromagnetism and are converted into paramagnetic substances. This temperature is called Curie temperature. This reduces the magnetic flux density to The magnitude of the required reverse magnetic field at zero is called coercive force. 1234789 The magnetic properties of the bulk nickel are as follows: Curie temperature is about 353. 0, and saturation magnetization is about 0.617. τ, the residual magnetization is about 0.300T, and the magnitude of the coercive force is about 239 A / m. So far, allotrope of nickel can be divided into face-centered cubic, FCC) metallic nickel with hexagonal close packed (HCP) metallic nickel. Almost common nickel powders are ferromagnetic substances with face-centered cubic crystal structure. Rarely A report on the preparation of nickel powder with the hexagonal close-packed crystal structure. Nickel powder with the hexagonal close-packed crystal structure has long been predicted to be also a ferromagnetic substance. According to Stoner theory, DA Papaconstantopoulos et al. It is predicted that nickel in the hexagonal close-packed crystal structure must be a ferromagnetic substance (see DA · Papaconstantopoulos, JL Fry, N · E. Brener, "Ferromagnetism in hexagonal close packed elements", Physical Review B, Vol. 39, No. 4, 1989 · 2 · 1, pp 2526-2528). As mentioned earlier, the most representative application of nickel powder is as an internal electrode in an electronic device. However, the conventional ferromagnetic nickel powder has the following Disadvantages: First, when the nickel powder contained in the electrode paste used to form the nickel internal electrode by printing method exhibits magnetic properties, the nickel powders will attract each other due to their magnetic properties to form a similar magnet (magnet) and magnetic block ( agglomerated) structure, making it difficult to form a uniform electrode paste. Secondly, with the development of mobile communications and computer technology, electronic devices have been using 1234789 °, so it is difficult to apply these materials to magnetic materials with high impedance at such high frequencies. These problems can be solved by using non-magnetic recording powder. SUMMARY OF THE INVENTION Accordingly, the present invention provides a method for making non-magnetic nickel powder. According to one aspect of the present invention, the method for making non-magnetic powder provided by the present invention includes the following steps: (a) heating-viewing compound, this ageing substance includes a precursor precursor compound (nickel precursor comp) and A polyhydric alcohol (p.0) to reduce the compound to a metal powder having a face-centered cubic crystal structure; and a mixture obtained by the heating step, to powder at least a part of the powder having a face-centered cubic crystal structure. Converted to a recording powder with a hexagonal close-packed crystal structure. [Embodiment] The present invention provides a method for manufacturing non-magnetic nickel powder, which includes the following steps: heating a mixture, which contains the recording precursor A compound and a polyhydric alcohol 'are used to combine this secretion compound_formerly a metal nickel powder having a face-centered cubic (FCQ day-to-day body structure); and (b) the mixture obtained in the heating step 加热 to combine at least a portion of The face-centered cubic crystal structure of the powder was converted into a nickel powder with a hexagonal close-packed crystal structure of 1234789. The nickel powder has been found in the study by Bu / ren, when-generally magnetic substances with FCC phase cover ~ When heated, it will be converted from rcc crystal structure to ㈣ ,,,, and., And the domain conversion is a mystery. 'Similar observation from the preparation of nickel precursor compounds, the production method known to this bet, that is, in ... Xiang Lizhi's subscription order Wei Weihe turned to FCC nickel dioxin and FCC powder in heated didorfanol to convert to HCP. The powder was combined into a series of one step. In short, the present invention provides-non Method of magnetic nickel powder. Although the present invention does not explain the principle of changing the structure of the powder in the polyol by heating, it is most likely because the metallic nickel dissolved in multiple revolutions will undergo recrystallization. Or the slave reaction. Even if there is no actual mechanism for phase transfer, the effectiveness of the present invention should not be affected by this. There is no relation to the pre-nickel compound, as long as it can be reduced by M alcohol to metallic nickel. All compounds can be used. For example, the precursor compounds include nickel oxides) or nickel nickel salts. Examples of nickel salts include sulfuric acid, nickel nitrate, nickel chloride, bromide, nickel fluoride, acetic acid, acetylacetonate, etc., and hydroxide. These nickel precursor compounds may be used alone or in combination. Xiyuan alcohol is used as a bath agent, and it is based on the pyrolysis nickel precursor compound. Polyols are also used as reducing agents to reduce nickel precursors to metallic nickel. Polyol is an alcohol compound 1234789. The compound ' has two or more hydroxyl groups (hydroxyl grup). An example of the use of a polyhydric alcohol as a reducing agent is described in U.S. Patent No. 4,539,04i. For example, the polyhydric alcohol may be a diol ((1101) fatty glycol or aliphatic glycol polyester (aliphatic glyeQi p () 1yeste) r;). Examples of the aliphatic glycol include: Alkylene glycols with C2-C6 as the main chain, such as ethylene glycol (jioi, propylene glycol), butanediol, pentanol pentanediol, hexanediol, and polyalkyleneglycois derived from alkylene glycols, such as polyethylene glycol ). In addition, examples of aliphatic glycols may further include diethylene glycol, triethylene glycoll and diprOpyiene glycol. Polyols may also be Glycerol (glycerol) is a triol (triol). However, the type of the polyol of the present invention is not limited to the above-mentioned polyols, and the above-mentioned polyols can be used alone or in combination. It is worth noting that the preferred types of polyols of the present invention are ethylene glycol, ethylene glycol, triethylene glycol, tetraethylene glycol, 丨, 2-propanediol 丨, 2), 1, 3-propanediol φΓ〇ρfferediol_1, 3), propylene glycol (dipropyleneglyco1), butanediol (butanediol_1, 2), 1, 3_ butanediol (butanediol-1, 3 ), 1,4-butanediol-1,4, or 2,3-butanediol-2,3. The initial content of the polyol in the mixture is not particularly limited and may depend on the solubility of the nickel precursor 1234789 compound. For example, the mixture may contain a specific amount of polyol such that the initial nickel precursor compound content is in the range of about 0.01 to 0.5 moles. To promote the reduction of the nickel precursor compound to metallic nickel, the method of the present invention includes heating a mixture containing the nickel precursor compound and a polyol. Here, "heating" means raising the temperature of a mixture containing a nickel precursor compound and a polyol to a temperature exceeding room temperature, and particularly a temperature exceeding about 20 ° C. In order to promote the side more effectively, the heating temperature is expected to be at least about 45. Generally speaking, when the heating temperature is more scaled, the county scale will be faster. However, when the -specific temperature is exceeded, the reduction rate does not increase any more. Also, it may cause the reactants to deteriorate. In this regard, the heating temperature may be about Gamma. C or lower. In step VII of the present invention, the composition of the mixture changes over time. -Initially, the mixture contains a silk drive compound and polymorphism. Before the lion drive compound is reduced to rcc__, the mixture will first contain both the precursor compound and the FCC phase. If the precursors other than the hydroxide precursor are contacted, the precursors will be partially converted to hydrogen and nickel, and reduced to impurities. The myeloid compounds of the hearing can be converted into gold powder without undergoing the first conversion to the oxidation step. After too much time has elapsed-substantially all of the nickel precursor compounds have been reduced to gold powder. As for the length of heating time, hemp lacks the warm sound of heating. 12 1234789 Those who are familiar with this technical field can easily know the heating time. Therefore, the length of this heating time is not an important factor in implementing the present invention. After the heating of the mixture of step (i) is performed, step (ii) is performed to convert the metallic nickel powder from the FCC phase to the HO > phase. In step ⑼, the scales have been subjected to the heating of the mixture of step ⑻. In step (b), if the temperature of the heating mixture is too low, the phase transfer of the nickel powder from the face-centered cubic crystal structure to the hexagonal closest-packed crystal structure may be hindered. If the heating temperature is too high, the phase transfer rate may no longer increase. And the polyol in the mixture may be decomposed by heating. Therefore, the heating temperature in step (b) may be in the range of about 38 ° C.
在本發明之-具體實施例中，使用一種具有回流冷卻(她X react.〇n vessd) ^ 步驟⑼之加熱溫度設定於接近多元醇的沸點_ing㈣。因加 =的溫度若較多元醇_點低許多，_粉的補移也許會不完 全。另-方面，加熱溫度若較多元醇滞點超過許多，則會有需要# 使用抗高壓岐應__生。因此，本發明步驟(响加熱溫 度賴最好約較多元醇_點高或低穴以内。其中較佳的是將步 驟⑼之混合物蝴至齡物巾的多辑轉的溫度。 ;γ驟(b)巾’右加熱混合物以供補移的時社短，錄粉之 FCC至HCP的相轉移也許不會發生。若時間太長，也許會產生錄 顆粒的*集，而且也許在轉移完全制輔著砂要的加熱。 13 1234789 因立此，在步驟(b)中加熱混合物以供相轉移之時間可為至少約时 鐘至約24小時。又’可使相轉移持續—段充分的時間，使得實質 上全部的FCC _錄粉轉換成Hcp相的鎳粉。關於特定反應條件 的相轉移時間，可輕易經測定而獲得。 當相轉移完成時，藉由-般使用於製備錄粉之清洗(丽啊 與乾燥(drying)的方式’將Hcp相的鎳粉從混合物中分離來。依 據本發明之綠製狀HCP_粉具有非離。如本發明之方 法製得之鎳粉，典型上可含有至少約1加％之Hcp鎳粉。 依據本發明之另一具體實施例，步驟(a)之混合物中更可另包 含有機鹼(organic base)、無機鹼(inorganic base)、或者兩者之混合 物。由實驗:得知，鎳前驅物化合物在酸驗值㈤^)在9至u中，最 容易還原為金屬鎳。有機鹼主要是用以調節混合物之酸鹼值至適 當值。 無機鹼可為鹼金屬之氫氧化物，例如NaOH及KOH。 有機驗之實例包括氫氧化四甲鏔(tetramethylammonium hydroxide，TMAH)、氫氧化四乙基銨(tetraethylammonium hydroxide， TEAH)、氫氧化四 丁基錄(tetrabutylammonium hydroxide，TBAH)、 氫氧化四丙基鏔(tetrapropylammonium hydroxide，TPAH)、氫氧化 苯甲基三甲基I安(benzyltrimethylammonium hydroxide)、 氫氧化二 曱基二乙基銨(dimethyldiethylammonium hydroxide)、氫氧化乙基 三曱基銨(ethyltrimethylammonium hydroxide)、氫氧化四 丁基碟 1234789 (tetrabutylphosphonium hydroxide)、三甲胺(trimethylamine，ΤΜΑ)、 一乙I女(diethylamine，DEA)、及乙醇胺(ethanolamine)，而前述之有 機鹼可以單獨或合併使用。 本發明之鹼在混合物中的含量並沒有特別限制。舉例來說， 驗可以為一特定含量，使得混合物的初始酸驗值到達約9或9以 上，更佳為10或10以上，以到達較佳的反應狀態。舉一更具說 明性的例子而言，若混合物中含有丨莫耳的鎳前驅物化合物，則 混合物中驗的初始含量可在約1至1〇莫耳的範圍内。 依據本發明之另一具體實施例，步驟(a)中的混合物更可包含 成核劑(nucleation agent)。成核劑用以讓還原後的金屬鎳粉沈澱， 以形成更均勻的顆粒大小。成核劑可為氯亞鉑酸鉀(K2ptCl4)、氯麵 酸鉀fHyPtCl6)、一氣化|巴(PdCl2)、或硝酸銀(AgN03)。混合物中的 成核劑的含量並沒有特別限制。例如混合物中若含有1莫耳的錦 前驅物化合物，則混合物中的成核劑的含量可為約1/1〇,〇〇〇至 2/1，000莫耳。一般而言，混合物中的成核劑的含量約為鎳前驅物 化合物的0.1°/〇。 下文中將以實例更清楚敘述本發明。然而，下列實例僅供說 明，而本發明當不僅侷限於此。 實施例 實施例 1 (TEG + TMAH) 15 1234789 於25〇毫升(ml)的三伸乙甘醇(TEG)中，溶解9〇·6克(g)的氫氣 化四甲銨(TMAH)，以製備成一第一溶液。於250毫升的三伸乙甘 醇中，溶解40克的Ni(CH3COO)2 · 4氏0 (醋酸鎳四水合），以製備 成一第二溶液。使用氯亞翻酸鉀做為成核劑，於2毫升的乙二醇 (ethylene glycol，EG)中，溶解 0.0664 克的氯亞鉑酸鉀(K2PtCl4)，以 製備成一第三溶液。將第一溶液、第二溶液、與第三溶液放置於 一具有回流冷卻器的反應器中，並攪拌。 使用裝備有磁攪拌子之加熱包(heating mantle)於190°C下將反⑩ 應器中之所得混合物加熱10分鐘，以製造FCC金屬鎳粉。於此 時，取所產生之FCC金屬鎳粉樣品予以離心，及然後以乙醇清洗。 將如此所獲得之FCC金屬鎳粉樣品於25°C之真空烘箱中乾燥過In a specific embodiment of the present invention, a heating method with reflux cooling (She X react. On Vessd) is used. The heating temperature of step 设定 is set close to the boiling point of the polyol. If the temperature of the additive is much lower than the polyol point, the make-up of the powder may be incomplete. On the other hand, if the heating temperature is much higher than the polyol's stagnation point, there will be a need to use anti-high pressure reaction. Therefore, the step of the present invention (the heating temperature is preferably about within the high or low point of the polyol point. Among them, the temperature at which the mixture of step ⑼ is converted to the temperature of the multi-folding of the aging towel is preferred. b) The time when the mixture is heated for supplementary transfer is short, and the phase transfer of FCC to HCP may not occur. If the time is too long, a * set of recorded particles may be generated, and the transfer may be completely controlled. 13 1234789 Therefore, the time for heating the mixture for phase transfer in step (b) can be at least about clock to about 24 hours. It can also continue the phase transfer for a sufficient time So that substantially all of the FCC powder can be converted into nickel powder of Hcp phase. The phase transition time of specific reaction conditions can be easily measured and obtained. When the phase transfer is completed, it is generally used to prepare the powder for recording. The method of washing (Liah and drying) 'separates the nickel powder of Hcp phase from the mixture. The green HCP powder according to the present invention has non-ionization. The nickel powder obtained by the method of the present invention is typically It can contain at least about 1 plus% of Hcp nickel powder. In another specific embodiment, the mixture in step (a) may further include an organic base, an inorganic base, or a mixture of the two. From experiments: it is known that the nickel precursor compound is in an acid. Test value ㈤) In 9 to u, it is easiest to reduce to metallic nickel. Organic bases are mainly used to adjust the pH value of the mixture to an appropriate value. Inorganic bases can be hydroxides of alkali metals, such as NaOH and KOH. Examples of organic tests include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TBAH) tetrapropylammonium hydroxide (TPAH), benzyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, ethyltrimethylammonium hydroxide, hydroxide Tetrabutylphosphonium 1234789 (tetrabutylphosphonium hydroxide), trimethylamine (TMA), diethylamine (DEA), and Alcohol amines (ethanolamine), and the base of the machine may have separately or in combination. The content of the base of the present invention in the mixture is not particularly limited. For example, the test may be a specific content such that the initial acid test value of the mixture reaches about 9 or more, more preferably 10 or more, to reach a better reaction state. As a more illustrative example, if the mixture contains a mole of nickel precursor compound, the initial content of the mixture may be in the range of about 1 to 10 moles. According to another embodiment of the present invention, the mixture in step (a) may further include a nucleation agent. The nucleating agent is used to precipitate the reduced metallic nickel powder to form a more uniform particle size. The nucleating agent may be potassium chloroplatinate (K2ptCl4), potassium chloride (fHyPtCl6), monogas | PdCl2, or silver nitrate (AgN03). The content of the nucleating agent in the mixture is not particularly limited. For example, if the mixture contains 1 mole of the precursor compound, the content of the nucleating agent in the mixture may be about 1 / 10,000 to 2 / 1,000 mole. Generally, the content of nucleating agent in the mixture is about 0.1 ° / 0 of the nickel precursor compound. Hereinafter, the present invention will be described more clearly with examples. However, the following examples are for illustration only, and the present invention should not be limited thereto. EXAMPLES Example 1 (TEG + TMAH) 15 1234789 In 25.0 milliliters (ml) of triethylene glycol (TEG), 90.6 g (g) of tetramethylammonium hydrogenate (TMAH) was dissolved to Prepare a first solution. In 250 ml of triethylene glycol, 40 g of Ni (CH3COO) 2 · 4'0 (nickel acetate tetrahydrate) was dissolved to prepare a second solution. Potassium chlorite was used as a nucleating agent, and 0.0664 g of potassium chloroplatinate (K2PtCl4) was dissolved in 2 ml of ethylene glycol (EG) to prepare a third solution. The first solution, the second solution, and the third solution were placed in a reactor having a reflux cooler and stirred. The resulting mixture in the reactor was heated at 190 ° C for 10 minutes using a heating mantle equipped with a magnetic stirrer to produce FCC metal nickel powder. At this time, a sample of the produced FCC metal nickel powder was centrifuged, and then washed with ethanol. The FCC metal nickel powder sample thus obtained was dried in a vacuum oven at 25 ° C.
夜。然後，以M0DEL4VSM 30 kOe (DMS股份有限公司）測定FCC 樣品之飽和磁化，得到24.0 emu/g。 然後，將混合物於原來的反應器中於220°C下加熱，及隨著時 間對錄粉取樣。將錄粉的樣品離心，及然後以乙醇清洗。將如此馨 所獲得之鎳粉樣品於25°C之真空烘箱中乾燥一夜。使用 X’PERT-MPD系統(飛利浦股份有限公司），於1〇。至9〇。的角度進 行樣品的X射線繞射(X-ray diffraction，XRD)分析，所得之结果 與時間的關係示於第1圖。如第1圖所示，於1至24小時之時間 歷程之時點所取的樣品均轉移至HCP相。且，測定各個樣品之飽 和磁化，得到0.030 emu/g (歷時1小時）、〇·〇28 emu/g (歷時2小 16 1234789 時）、0.027 emu/g (歷時 3 小時）、0.020 emu/g (歷時 4 小時）、0·019 emu/g (歷時 5 小時）、0·019 emu/g (歷時 6 小時）、0.018 emu/g (歷 時7小時)、0.018 emu/g (歷時8小時)、〇·〇ΐ9 emu/g (歷時9小時）、 0·018 emu/g (歷時10小時）、〇·〇ΐ8 emu/g (歷時24小時）。即，當鎳 粉之結晶相自FCC轉移成HCP時，鎳粉之飽和磁化降低至FCC 之約1A200。自實施例1所製備之FCC與HCP鎳粉之顆粒具有 約180nm之平均粒徑，且為球狀。 實施例 2(DEG + TMAH) 溶解90·6克的氫氧化四甲銨(TMAH)於250毫升的二伸乙甘 醇(DEG)中，以製備成一第一溶液。溶解30克的Ni(CH3COO)2 · 4H2〇於250氅升的DEG中’以製備成一第二溶液。以氯亞銘酸 鉀為成核劑(nucleation agent)，溶解0.0249克的氯亞鉑酸鉀於2毫 升的乙二醇中，以製備成一第三溶液。將第一溶液、第二溶液、 與第三溶液放置於一備有回流冷卻器的反應器中，並攪拌。 使用裝備有磁攪拌子之加熱包於190°C下將反應器中之所得 混合物加熱40分鐘，以製造FCC金屬鎳粉。將所製得之FCC金 屬鎳粉予以離心，及然後以乙醇清洗。將如此所獲得之FCC金屬 鎳粉於25°C之真空烘箱中乾燥過夜。測得FCC鎳粉之飽和磁化為 24.2 emu/g 〇 然後，將混合物於原來的反應器中於22〇°C下加熱，及隨著時 17 1234789 間對鎳粉取樣。將鎳粉的樣品離^，及織以乙醇清洗。將如此 所獲得之鎳粉樣品於25°C之真空烘箱中乾燥一夜。於1〇。至9〇。 的角度進行樣品❸X射線繞射(XRD)分析，所得之結果與時間的 關係示於第2圖。樣品中具有HCP晶體結構的鎳粉分率為1〇 (歷時1小時）、18 wt% (歷時2小時）、29加％ (歷時3小時）、及 35 wt/〇 (歷日守4小時）。樣品之飽和磁化值為23·4 emu/g (歷時J小 日Ο、22·8 emu/g (歷時 2 小時）、21.7 emu/g (歷時 3 小時）、及 21·〇 emu/g (歷時4小時)。此等值低於上述FCC鎳粉之飽和磁化值(μ emu/g)。自實施例2所製備之咖與Hcp錄粉之顆粒具有約施瓜 之平均粒徑，且為球狀。 實施例 3(DEG + TMAH) 將含有10克的2·5Μ氫氧化鈉水溶液、0 054克的氯亞鉑酸 鉀5〇〇 ml的二伸乙甘醇、及3〇克的Ni(CH3C〇〇)2 · 4托〇的混 合物放置於一備有回流冷卻器的反應器中，並攪拌。 將混合物於反應器中於19(TC下加熱3〇分鐘，以製造FCC金 屬鎳粉。然後，將同一反應器中之混合物於19(rc下加熱24小時， 以進仃鎳粉之相轉移。然後，將鎳粉離心及以乙醇清洗。將如此 所獲得之鎳粉於25°C之真空烘箱中乾燥過夜。 然後，對於如此所得之鎳粉進行χ_射線繞射(Xjy^)分析，結 果示於弟3圖。鎳粉的HCP分率為1⑻加％。測得鎳粉的飽和磁 1234789 化值為〇·〇3 emu/g。以掃描式電子顯微鏡(scanning eiectr0I1 microscope，SEM)觀察，顯示鎳粉之顆粒具有約uonm之平均粒 徑，且為球狀。 實施例4 (EG) 將含有〇·〇54克的氯亞鉑酸鉀、5〇〇 mi的乙二醇、及3〇克的 Ni(CH3COO)2 · 4托0之混合物放置於一備有回流冷卻器的反應器 中，並攪拌。 將混合物於反應器中於190°C下力tr熱1小時，以製造j?cc金 屬鎳粉。對於此FCC鎳粉進行XRD分析，結果示於第4圖。鎳 粉的FCC分率為1〇〇 wt°/〇。測得此FCC鎳粉的飽和磁化值為24.5 emu/g ° 接著，將混合物於原來的反應器中於19(rc下加熱24小時， 以進行鎳粉之轉移。織，將鎳粉離心、，並以乙醇清洗。將如 此所獲得之騎於坑之A魏箱巾乾燥過夜。 J後對於如此所得之錄粉進行χ_射線繞射⑽分析，結 果示於第5圖。錄粉的HCP分率為55痛。測得錦粉的飽和磁化 值為18.5刪/g。以觀觀察，顯示錦粉之顆粒具有約偷〇之 平均粒徑，且為半球狀。 而上述可清楚地瞭解，依據本發明之方法，可輕易製得具六 方最孩堆積(HCP)曰曰曰體結構的非磁性鎳粉。 19 1234789 以上所述僅為本發明之較佳實施例，凡依本發明申請專利範 圍所做之均等變化與修飾，皆應屬本發明專利之涵蓋範圍。 【圖式簡單說明】 第1圖為依據本發明之實施例之金屬鎳粉之χ射線繞 分析結果。 第2圖為依據本發明之另—實補之金屬鎳粉之χ射線繞射 (XRD)分析結果。 第3圖為依據本發明之另一實施例之金屬秦粉之腦分析結 果。 第4圖為本發明之另—實施例之中間物(咖金屬鎳粉)之 XRD分析結果。 第5圖為第4圖之實施例所得含有HCP之金屬驗之最終產 物之XRD分析結果。 【主要元件符號說明】 本案圖式無元件符號。 20night. Then, the saturation magnetization of the FCC sample was measured with MODEL4VSM 30 kOe (DMS Co., Ltd.) to obtain 24.0 emu / g. The mixture was then heated in the original reactor at 220 ° C, and the dusting was sampled over time. The powdered sample was centrifuged and then washed with ethanol. The nickel powder sample thus obtained was dried in a vacuum oven at 25 ° C overnight. X'PERT-MPD system (Philips Co., Ltd.) was used. To 90. The X-ray diffraction (XRD) analysis of the sample was performed at an angle of 90 °, and the relationship between the results obtained and time is shown in Figure 1. As shown in Figure 1, all samples taken at the time point of the 1-24 hour time course were transferred to the HCP phase. The saturation magnetization of each sample was measured to obtain 0.030 emu / g (for 1 hour), 0.028 emu / g (for 2 hours, 16 1234789 hours), 0.027 emu / g (for 3 hours), and 0.020 emu / g. (4 hours), 0.019 emu / g (5 hours), 0.019 emu / g (6 hours), 0.018 emu / g (7 hours), 0.018 emu / g (8 hours), 0.08 emu / g (for 9 hours), 0.018 emu / g (for 10 hours), 0.80 emu / g (for 24 hours). That is, when the crystalline phase of the nickel powder is transferred from the FCC to HCP, the saturation magnetization of the nickel powder is reduced to about 1A200 of the FCC. The particles of the FCC and HCP nickel powders prepared from Example 1 had an average particle diameter of about 180 nm and were spherical. Example 2 (DEG + TMAH) 90.6 g of tetramethylammonium hydroxide (TMAH) was dissolved in 250 ml of ethylene glycol (DEG) to prepare a first solution. 30 g of Ni (CH3COO) 2. 4H2O was dissolved in 250 liters of DEG 'to prepare a second solution. Using potassium chlorinate as a nucleation agent, 0.0249 g of potassium chloroplatinate was dissolved in 2 ml of ethylene glycol to prepare a third solution. The first solution, the second solution, and the third solution were placed in a reactor equipped with a reflux cooler and stirred. The obtained mixture in the reactor was heated at 190 ° C for 40 minutes using a heating bag equipped with a magnetic stir bar to produce FCC metal nickel powder. The obtained FCC metal nickel powder was centrifuged and then washed with ethanol. The FCC metal nickel powder thus obtained was dried in a vacuum oven at 25 ° C overnight. The saturation magnetization of the FCC nickel powder was measured to be 24.2 emu / g. Then, the mixture was heated at 22 ° C. in the original reactor, and the nickel powder was sampled over 17 1234789. The nickel powder samples were separated and woven with ethanol. The nickel powder sample thus obtained was dried overnight in a vacuum oven at 25 ° C. At 10. To 90. The X-ray diffraction (XRD) analysis of the sample was performed at an angle of 90 °, and the relationship between the obtained results and time is shown in FIG. 2. The nickel powder with HCP crystal structure in the sample was 10 (for 1 hour), 18 wt% (for 2 hours), 29% (for 3 hours), and 35 wt / 〇 (for 4 hours). . The saturation magnetization values of the samples were 23.4 emu / g (lasted J small day 〇, 22.8 emu / g (lasted 2 hours), 21.7 emu / g (lasted 3 hours), and 21.7 emu / g (lasted 4 hours). These values are lower than the saturation magnetization value (μ emu / g) of the above FCC nickel powder. The granules of the coffee and Hcp powder prepared from Example 2 have an average particle size of about 1500 g, and are spheres. Example 3 (DEG + TMAH) A solution containing 10 g of a 2.5 M aqueous sodium hydroxide solution, 0 054 g of potassium chloroplatinate, 500 ml of diethylene glycol, and 30 g of Ni ( The mixture of CH3C00) 2 · 4 Torr was placed in a reactor equipped with a reflux cooler and stirred. The mixture was heated in the reactor at 19 ° C for 30 minutes to produce FCC metal nickel powder. Then, the mixture in the same reactor was heated at 19 ° C for 24 hours to transfer the phase of nickel powder. Then, the nickel powder was centrifuged and washed with ethanol. The nickel powder thus obtained was heated at 25 ° C. Dry in a vacuum oven overnight. Then, the X-ray diffraction (Xjy ^) analysis was performed on the nickel powder thus obtained, and the results are shown in Figure 3. The HCP score of the nickel powder was 1% plus%. The saturation magnetic value of the obtained nickel powder was 1234789 emu / g. Observation with a scanning electron microscope (SEM) revealed that the particles of the nickel powder had an average particle diameter of about uonm and were spherical. Example 4 (EG) A mixture containing 0.054 g of potassium chloroplatinate, 500 g of ethylene glycol, and 30 g of Ni (CH3COO) 2.4 Torr was placed in a container prepared with The reactor of the reflux cooler was stirred, and the mixture was heated in the reactor at 190 ° C for 1 hour to produce j? Cc metal nickel powder. XRD analysis was performed on the FCC nickel powder, and the results are shown in section Figure 4. The FCC fraction of nickel powder is 100wt ° / 〇. The saturation magnetization value of this FCC nickel powder was measured to be 24.5 emu / g °. Next, the mixture was heated in the original reactor at 19 (rc). 24 hours to transfer the nickel powder. Weaving, centrifuging the nickel powder, and washing it with ethanol. The A Wei box towel riding in the pit thus obtained was dried overnight. After the J, the powder thus obtained was subjected to χ_ The analysis of the diffracted rays is shown in Fig. 5. The HCP score of the recorded powder is 55 Pain. The saturation magnetization value of the measured powder is 18.5 deleted / g. From observation, it is shown that the particles of the brocade powder have an average particle diameter of about 0 and are hemispherical. And the above can be clearly understood that according to the method of the present invention, a hexagonal child heap (HCP) can be easily prepared. Non-magnetic nickel powder with a bulk structure. 19 1234789 The above is only a preferred embodiment of the present invention, and any equivalent changes and modifications made in accordance with the scope of the patent application for the present invention shall fall within the scope of the patent for the present invention. [Brief description of the drawings] Fig. 1 is a result of X-ray diffraction analysis of a metallic nickel powder according to an embodiment of the present invention. Fig. 2 is a result of X-ray diffraction (XRD) analysis of another supplemented metallic nickel powder according to the present invention. Fig. 3 is a result of brain analysis of metal Qin powder according to another embodiment of the present invention. Fig. 4 is an XRD analysis result of an intermediate (nickel metal powder) of another embodiment of the present invention. Fig. 5 is an XRD analysis result of the final product of the metal test containing HCP obtained in the example of Fig. 4. [Description of main component symbols] There are no component symbols in the drawings of this case. 20