TWI750667B - 貴金屬合金之製造方法及由此獲得之貴金屬合金 - Google Patents
貴金屬合金之製造方法及由此獲得之貴金屬合金 Download PDFInfo
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Abstract
本發明係關於製造自貴金屬硼化物形成的合金之方法,該方法涉及使該貴金屬源與硼源於熔融狀態之鹽或鹽的混合物中反應。本發明亦關於自貴金屬硼化物形成的合金,該合金包含Mx
By
之結晶奈米粒子,其中貴金屬M分布於B之非晶形基質中或分布於B及Mz
Ba
之非晶形基質中。
Description
本發明係關於製造貴金屬合金之方法。本發明亦關於此貴金屬合金以及以該等合金製成之部件。特別是,本發明係關於製造由金、銀、鉑、鈀、釕或銥所獲得之貴金屬輕合金之方法。此處所談論之貴金屬輕合金係可滴定的,亦即,彼等為合金,其進入合金之組成中的貴金屬之質量與該合金之總質量之間的比係由定律決定。
就本發明及下文之意義來說,貴金屬意指選自由由下列所組成之群組中之金屬:金、銀、鉑、鈀、釕及銥。
諸如金之貴金屬係用於眾多領域,諸如首飾及鐘錶。金的缺點係容易容易變形,其結果是簡單衝擊就足以令使用該貴金屬製成的首飾變形。這是為何很早就尋求藉由將金與其他金屬元件合金化以改善其機械性質的原因。在這方面,銀及銅為用以改善金之剛性的兩種主要金屬。金與諸如銀或銅之其他金屬元素合金化產生硬度大於金之硬度的金屬合金。不過,該等金之合金具有高密度之缺點。這是為何嘗試使金與具有較低密度之金屬元素合金化的原因。
已進行試驗試圖使為重金屬(亦即,密度高(大約19.3g.cm-3
)之金屬)之金(Au)與為非常輕的金屬(亦即,密度低(大約2.3g.cm-3
)之硼(B)合金化。不過,迄今所進行之試圖使金與硼合金化的嘗試均以失敗告終,或者最佳係導致極低之硼溶解率,無法預期用於工業生產。事實證明由金及硼之組合所形成的材料為不安定的,以及使用該組合結果無法產生可滴定的大量組分,諸如18K金。該等問題特別可以藉由熔融元素以合金化之習用方法期間無法混合金與硼的事實來解釋。確實,因金之高密度緣故,其具有沉降於坩堝底部的傾向,而具有較低密度的硼會上浮。
因此,眾多文件(諸如Handbook of Solid State Chemistry(第一版,Richard Dronskowski、Shinichi Kikkawa、及Andreas Stein編,於2017出版)第10章論及不可能產生富含硼之貴金屬硼化物,即(Mx
By
金屬硼化物),其中M為金屬且y與x之比率大於或等於1。
例如,於鈀之情況下,可獲得硼含量不超過Pd6
B至Pd2
B之金屬硼化物。就鉑而言,可獲得PtB0.7
,其為富含硼之金屬硼化物的下限。就18K金(亦即含有75質量%之金)而言,必須具有接近或等於AuB5.7
之組成,據申請人所知,目前尚未實現該組成。
本發明目的係提供製造貴金屬輕合金之方法,該方法特別能獲得由物理化學觀點來看為安定之貴金屬輕合金以及使用彼可產生大量組分。更精確地說,根據本發明之方法涉及藉由貴金屬源與硼源於作為溶劑之熔鹽的混合物中反應而產生貴金屬與硼之合金。較佳的,硼源為硼氫化鈉,而貴金屬源為該貴金屬之氯化物。來自該方法之合金係藉由將貴金屬硼化物Mx
By
(其中,M為貴金屬)之奈米粒子分布於硼B之基質中所形成。較佳的,貴金屬硼化物Mx
By
之奈米粒子的y/x比係大於或等於1,更佳係大於或等於2。因此,根據本發明之方法能產生富含硼之貴金屬合金。
根據本發明之實施態樣,貴金屬與硼之合金係經由粉末冶金而直接用以製造部件。
根據本發明另一實施態樣,來自根據本發明之於熔鹽中合成之方法的貴金屬與硼之合金在藉由粉末冶金製造部件之前用貴金屬增濃。
因此,本發明係關於直接來自藉由於熔鹽中合成之製造方法的貴金屬與硼之合金以及用貴金屬增濃之合金。本發明亦關於以直接來自藉由於熔鹽中反應之製造方法的貴金屬與硼之合金或用貴金屬增濃之該相同合金所製成的部件,特別是鐘錶或首飾。確實,y/x比太大可能無法產生例如18K金。在該情況下,使硼之基質用該貴金屬增濃。
根據本發明之方法能獲得兼具優異的機械性質以及低密度之貴金屬與硼之合金。據申請人所知,本發明之方法首次提供以工業規模使具有極低密度之組分(於本情況為硼)與貴金屬(特別是但不僅限於高密度之金)合金化的可能性。值得注意的是,在根據本發明之方法中,所選擇之貴金屬與硼緊密地合金化,無法觀察到兩種材料之間的偏析現象。
本發明係關於製造貴金屬硼化物(下文亦稱為貴金屬與硼之合金)之方法,以及由該合金製造部件之方法。合金係藉由於熔鹽中之合成製造,一種亦以盎格魯-撒克遜名而聞名之合成,稱為於熔鹽中合成(Synthesis in Molten Salts或SMS)。該合成涉及在貴金屬及硼之反應性物質彼此存在之下將彼等置入包含鹽之介質。於整體加熱時,鹽會熔融因而表現得像液態介質。於熔鹽中合成貴金屬與硼之合金使用金屬源及硼源。金屬源可選自包含下列之群組:貴金屬之硫酸鹽、碳酸鹽、乙酸鹽、硝酸鹽、乙醯丙酮化物及鹵化物。較佳的,貴金屬源為鹵化物,以及更精確地說,為貴金屬之氯化物(MClx
)。貴金屬係選自金(Au)、銀(Ag)、鉑(Pt)、鈀(Pd)、釕(Rh)及銥(Ir),更佳係選自金、銀、鉑及銥。硼源可選自包含硼烷(Bx
Hy
)及硼氫化物(MBH4
)之群組。較佳的,硼源為硼氫化鈉(NaBH4
)。因此,反應較佳係於貴金屬之氯化物(諸如金(Au)之AuCl3
)以及硼氫化鈉(NaBH4
)存在之下進行。關於用作反應介質之鹽,彼等較佳可溶於水以使能於反應之後回收硼化物。例如,此可為鹼金屬之一或多種鹽的混合物,更精確地說為鹵化物、碳酸鹽、硫酸鹽或硝酸鹽的混合物。較佳的,此可為比率為45至50重量%之LiCl與55至50重量%之KCl的氯化鋰與氯化鉀之共熔混合物,其熔點為大約355℃。該鹽較佳存在莫耳量係大於硼源中之硼與貴金屬源中之金屬的總莫耳量。
該鹽於周圍溫度下通常為固態以及於反應期間於100與1000℃之間、較佳於355與900℃之間的溫度下熔融。理想的,此高於鹽之混合物的熔融溫度,但低於該混合物的汽化溫度。例如,混合物LiI/KI於超過850℃部分汽化。
此外,反應介質可視情況包括具有控制粒子大小及/或所獲得之硼化物的形態之功能的一或多種添加劑。此可為例如碘化物,諸如碘化鉀或碘化鈉。添加劑之量較佳係每莫耳貴金屬源中之金屬為在1與100莫耳之間。
該方法可於周圍壓力下或於大於周圍壓力之壓力下進行。氣氛可受控制。因此,因該等化學產物對於水及/或對於氧的敏感性緣故,使用鋰鹽或鉀鹽需要在惰性氣氛之下作業。因此,前驅物係於氬之惰性氣氛之下操作及混合。有鑑於氮能與硼的一些物質反應以及導致形成氮化硼,合成本身係在氬及非氮之氣氛之下進行。
該方法係藉由混合貴金屬源、硼源及鹽而進行。將整體加熱至所欲溫度以熔融鹽或鹽之混合物並於該溫度下維持較佳在30分鐘與10小時之間的時間。於反應之後,使反應介質冷卻,較佳係自然冷卻。獲得呈分散於一體積之固態鹽中的凝集物形式之金屬之硼化物。為消除鹽,於諸如水或甲醇之極性溶劑中進行數回合洗滌/離心。
來自於熔鹽中製造之方法的合金係呈由分散於非晶形硼B之基質中的金屬硼化物Mx
By
之結晶奈米粒子的凝集物所形成之粉末形式。奈米級粒子意指大小在5與200 nm之間、較佳在10與100 nm之間的粒子。凝集物通常具有在0.3與1微米之間的大小。較佳係,構成結晶奈米粒子之金屬硼化物Mx
By
的化學計量y/x比係大於或等於1、更佳係大於或等於2。因此,就18K金之合金而而,奈米粒子必須對應於y接近6之組成AuBy
。
根據本發明第一實施態樣,來自藉由於熔鹽中合成之製造方法的合金係直接用於藉由粉末冶金製造部件。由凝集物所形成之粉末係以此狀態使用或事先研磨以獲得D50小於70 μm之粉末。換言之,50%之形成粉末的粒子具有小於或等於70 μm之直徑。
根據本發明第二實施態樣,在藉由粉末冶金製造部件之前使合金用貴金屬增濃。該增濃係經由涉及下列之額外步驟進行:
-提供一數量之上述合金的粉末,該粉末可直接來自於熔鹽中合成之方法或可研磨以達D50小於70 μm;
-提供一數量之貴金屬的粉末。此可為與藉由於熔鹽中合成所獲得之合金的貴金屬相同之貴金屬。亦可以使合金用其他貴金屬或用貴金屬之混合物增濃。該粉末具有小於70 μm之D50;
-將這兩量之粉末混合並如下述燒結所得之混合物,以於燒結之後獲得包含金屬硼化物Mx
By
(其中M為貴金屬)之結晶奈米粒子分布於由非晶形硼B及金屬硼化物Mz
Ba
(其中z及a分別可等於或小於x及y)所形成之基質中的合金。應注意的是分布於硼之基質中的金屬硼化物粒子的化學計量通常與形成具有硼之基質的金屬硼化物粒子之化學計量不同。形成具有硼之基質的金屬硼化物粒子的金屬之莫耳分率z經常等於或甚至略大於硼之莫耳分率a。
已指出於該步驟期間可將諸如例如鎳之除貴金屬以外的元素添加至混合物。
不論係用根據第一替代方案之合金或用根據第二替代方案之合金,製造部件之方法可包括下列步驟:
-藉由施加單軸壓力壓實粉末;
-於0.5 GPa與10 GPa之間的壓力下對該壓實之粉末進行火花電漿燒結(或快速燒結),或者在80巴與2200巴之間的壓力下進行熱均壓(或HIP)處理,該處理係於400℃與2100℃之間的溫度下進行以獲得至少一塊貴金屬與硼之合金錠;
-機械加工貴金屬與硼之合金錠以獲得所欲部件,或
-藉由微粉化處理將貴金屬與硼之合金錠還原至粉末狀態,以及藉由處理將從微粉化處理所形成之粉末而獲得所欲部件。
一旦貴金屬與硼之合金錠經微粉化,獲得所欲塊狀部件的第一種可能涉及將從微粉化處理所形成之粉末引入模具並使該模具經受單軸或均壓。
一旦貴金屬與硼之合金錠經微粉化,獲得所欲塊狀部件的第二種可能涉及對從微粉化處理所形成之粉末進行三維積層製造處理。
三維積層製造處理可為直接列印型。直接型三維積層製造之可用技術為雷射燒結,亦以盎格魯-撒克遜名稱稱為選擇性雷射熔融(Selective Laser Melting或SLM),以及電子轟擊,亦以盎格魯-撒克遜名稱稱為電子束熔融。
三維積層製造處理可為間接列印型。間接型三維積層製造之可用技術為:
-噴墨印刷(噴墨):將從貴金屬與硼之合金錠的微粉化處理所形成之粉末分散於墨水中。一層又一層印刷該墨水,各層係在沉積下一層之前藉由曝露於例如UV光之輻射源而硬化。
-奈米粒子噴射(NPJ):該技術(特別是由XJet公司所研發者)與經由噴射液態墨水印刷相似,其差異在於該墨水係由從微粉化處理所形成之於懸浮液中的奈米粒子構成。然後發射該懸浮液,然後逐層乾燥。
-數位光投影(DLP):該技術涉及藉由於鏡子上的反射將欲結構化之部件的影像投影至含有分散於光聚合物中之從微粉化處理所形成之粉末的粒子之粉末床上。
一旦貴金屬與硼之合金錠經微粉化,獲得所欲塊狀部件的第三種可能涉及於聚合物黏合劑存在之下對從該錠之微粉化處理所形成的粉末進行射三維積層製造處理或微噴射三維積層製造處理。因此,將從貴金屬與硼之合金錠的微粉化處理所形成之粉末與聚合物黏合劑混合以獲得原料。然後藉由對原料進行噴射或微噴射或者進行積層製造之技術而產生生坯,其形狀對應於該所欲部件之輪廓。
於聚合物黏合劑存在下積層製造之間接可用技術當中,可提及下列:
-顆粒上溶劑噴射:該技術涉及將溶劑發射至以原料所形成之顆粒床上。顆粒之尺寸為大約10 μm至50 μm。逐層印刷所欲部件,顆粒經由黏合劑團聚。
-FFD(熔絲沉積):尺寸在毫米範圍之長絲係藉由團聚原料所生產。然後加熱長絲以及製成彼之材料從噴嘴逸出,該噴嘴之直徑為大約40 μm以及能以三維列印所欲部件。
-微擠出。
或者,藉由使用涉及將含有溶劑及黏合劑之墨水噴流投射至由從微粉化處理所形成之粉末的粒子所形成之粉末床上的黏合劑噴射技術而可於積層製造期間直接產生黏合劑與粉末之間的混合物。
就黏合劑而言,可選自由下列所形成之群組:聚乙二醇(PEG)、乙酸丁酸纖維素(CAB)、奈米纖維素(纖維素之奈米級衍生物)、玉米澱粉、糖、聚乳酸(或PLA)、聚乙烯、聚丙烯、合成或天然蠟及硬脂酸。
藉由對生坯進行稱為脫膠步驟之消除聚合物黏合劑的步驟而獲得棕色體,於該步驟期間生坯係經化學處理,然後於爐中熱處理以燒除殘餘聚合物黏合劑,該脫膠步驟通常係以氣相於硝酸或草酸氣氛中且於100℃與140℃之間的溫度下進行。
最後,在保護性氣氛之下且於700℃與1800℃之間的溫度下對棕色體進行燒結處理以獲得所欲部件。
應注意的是,在燒結處理之後,可在500巴與2200巴之間的壓力之下且在600℃與2100℃之間的溫度下,經由熱均壓(或HIP)對該來自燒結步驟的部件進行後處理步驟。
如此製造之部件係從貴金屬硼化物所製成之合金製造。根據第一替代方案,合金係由Mx
By
之結晶奈米粒子形成,其中M為分布於B硼之非晶形基質中的貴金屬。根據第二替代方案,用貴金屬增濃之合金包括分布於硼B與貴金屬之硼化物Mz
Ba
之非晶形基質中的Mx
By
之結晶奈米粒子。貴金屬M係選自金(Au)、銀(Ag)、鉑(Pt)、鈀(Pd)、釕(Rh)及銥(Ir)。較佳的,其係選自金、銀、鉑、及銥,更佳係其為金。較佳的,Mx
By
奈米粒子之y/x比係大於或等於1,更佳的,其係大於或等於2。至於a/z比,其通常小於或等於1。
此處所談論之貴金屬輕合金係可滴定的,亦即,彼等為合金,其進入合金之組成中的貴金屬之質量與該合金之總質量之間的比係由定律判定。經由本發明方法所獲得之出色的貴金屬合金為具有組成AuB 6
且密度在6.6與7g/cm3
之間的金與硼之18K合金。亦應注意本發明內容中所使用之金粉末較佳為24K亮1/2黃色金之粉末。
部件可特別為鐘錶或首飾,以及更精確地說,外部部件,諸如中間、底部、邊框、按鈕、腕帶、錶盤、指針、錶盤刻度等。
不用說,本發明不限於已描述之實施態樣,以及對熟習本領域之人士而言,在不超出附錄申請專利範圍所界定之本發明內容的情況下可有各種樣本修改及替代方案。
Claims (28)
- 一種製造貴金屬與硼之合金粉末以獲得貴金屬硼化物之方法,該貴金屬係選自由下列所組成之群組:金、銀、鉑、鈀、釕及銥,該方法涉及使該貴金屬源與硼源於呈熔融狀態之一或多種鹽中反應,以及基於該目的包含下列步驟:- 混合該硼源、該貴金屬源及呈固態之該鹽(類);- 將該混合物加熱至介於100與1000℃之間之溫度,以使該硼源與該貴金屬源反應以獲得該貴金屬之金屬硼化物;- 冷卻該混合物;- 自該貴金屬硼化物分離該固化之鹽(類),該貴金屬硼化物係呈包括由分布於非晶形硼B之基質中的貴金屬硼化物MxBy之結晶奈米粒子所形成的凝集物的粉末形式,該貴金屬硼化物MxBy之結晶奈米粒子的y/x比係大於或等於1。
- 如請求項1之製造合金粉末之方法,其中,將該混合物加熱至介於355與900℃之間之溫度,以使該硼源與該貴金屬源反應以獲得該貴金屬之金屬硼化物。
- 如請求項1之製造合金粉末之方法,其中,該貴金屬硼化物MxBy之結晶奈米粒子的y/x比係大於或等於2。
- 如請求項1之製造合金粉末之方法,其中,該貴金屬源係選自由下列所組成之群組:該貴金屬之 硫酸鹽、碳酸鹽、乙酸鹽、硝酸鹽、乙醯丙酮化物及鹵化物。
- 如請求項4之製造合金粉末之方法,其中,該貴金屬源為貴金屬之氯化物MC1x,其中M為該貴金屬。
- 如請求項1之製造合金粉末之方法,其中,該硼源係選自由硼烷及硼氫化物所形成之群組。
- 如請求項6之製造合金粉末之方法,其中,該硼源為硼氫化鈉NaBH4。
- 如請求項1至7中任一項之製造合金粉末之方法,其中,其包括用於修改該貴金屬硼化物的組成之下列額外步驟:- 提供至少一數量之該貴金屬粉末及/或另一貴金屬粉末;- 提供一數量之該貴金屬硼化物粉末;- 混合該貴金屬粉末及/或該其他貴金屬粉末與該貴金屬硼化物粉末以獲得該貴金屬硼化物與該貴金屬及/或與該其他貴金屬之混合物。
- 如請求項8之製造合金粉末之方法,其中,該貴金屬粉末及/或該其他貴金屬粉末具有小於70μm之d50,以及該貴金屬硼化物粉末具有小於70μm之d50。
- 一種使用經由如請求項1至9中任一項之製造合金粉末之方法所獲得的貴金屬硼化物製造部件之方法,其特徵在於其包含下列步驟: - 提供貴金屬硼化物粉末;- 藉由施加單軸壓力壓實該貴金屬硼化物粉末與該貴金屬粉末之混合物;- 於0.5GPa與10GPa之間的壓力下對該壓實之粉末進行火花電漿燒結(spark plasma sintering),亦稱為快速燒結(flash sintering),或者在80巴(bar)與2200巴之間的壓力下進行熱均壓(亦稱為HIP(hot isostatic pressing))處理,該處理係於400℃與2100℃之間的溫度下進行以獲得至少一塊該貴金屬硼化物之合金錠;以及- 機械加工該錠以獲得所欲部件,或- 藉由微粉化處理將該錠還原至粉末狀態,以及藉由處理將從該微粉化處理所形成之該粉末而獲得所欲部件。
- 如請求項10之製造部件之方法,其中,為獲得該所欲部件,將從該微粉化處理所形成之該粉末引入模具以及經受單軸或均壓。
- 如請求項10之製造部件之方法,其中,為了產生該所欲部件,對從該微粉化處理所形成之該粉末進行三維積層製造(three-dimensional additive manufacturing)。
- 如請求項12之製造部件之方法,其中,該三維積層製造為直接列印型,其係選自由稱為選擇性雷射熔融(Selective Laser Melting)或縮寫形式為SLM之雷射燒結及藉由稱為電子束熔融之電子轟擊的燒結所形成的群組。
- 如請求項12之製造部件之方法,其中,該三維積層製造之處理為間接列印型,其係選自由噴墨、奈米粒子噴射(NanoParticle Jetting)及數位光投影(Digital Light Projecting)所形成的群組。
- 如請求項10之製造部件之方法,其中,為了產生該所欲部件,於聚合物黏合劑存在之下對從該微粉化處理所形成之該粉末進行噴射三維積層製造處理或微噴射三維積層製造處理。
- 如請求項15之製造部件之方法,其中,該方法包含下列步驟:- 混合從該錠之該微粉化處理所形成的該粉末與該聚合物黏合劑以獲得原料;- 藉由對該原料進行噴射或微噴射而產生生坯,其形狀對應於該所欲部件之輪廓;- 對該生坯進行稱為脫膠(debinding)步驟之消除該聚合物黏合劑的步驟而獲得棕色體(brown body),於該步驟期間該生坯係經化學處理,然後於爐中熱處理以燒除殘餘聚合物黏合劑,該脫膠步驟係以氣相於硝酸或草酸氣氛中且於100℃與140℃之間的溫度下進行;- 在保護性氣氛之下且於700℃與1800℃之間的溫度下對該棕色體進行燒結處理以獲得該所欲部件。
- 如請求項15之製造部件之方法,其中,該方法包含下列步驟:- 藉由對該錠之該微粉化處理所形成的該粉末進行該 三維積層製造處理而產生生坯,其形狀對應於該所欲部件之輪廓;- 對該生坯進行稱為脫膠步驟之消除該聚合物黏合劑的步驟而獲得棕色體,於該步驟期間該生坯係經化學處理,然後於爐中熱處理以燒除殘餘聚合物黏合劑,該脫膠步驟係以氣相於硝酸或草酸氣氛中且於100℃與140℃之間的溫度下進行;- 在保護性氣氛之下且於700℃與1800℃之間的溫度下對該棕色體進行燒結處理以獲得該所欲部件。
- 如請求項17之製造部件之方法,其中,該積層製造之技術係選自由顆粒上溶劑噴射(solvent on granulate jetting)、熔絲沉積(fused filament deposition)及微擠出(micro-extrusion)所形成的群組。
- 如請求項17之製造部件之方法,其中,該積層製造之技術為黏合劑噴射。
- 如請求項16之製造部件之方法,其中,在該燒結處理之後,藉由在500巴與2200巴之間的壓力下以及在600℃與2100℃之間的溫度下之縮寫形式稱為HIP的熱均壓對來自該燒結步驟之該部件進行後處理步驟。
- 如請求項17之製造部件之方法,其中,在該燒結處理之後,藉由在500巴與2200巴之間的壓力下以及在600℃與2100℃之間的溫度下之縮寫形式稱為HIP的熱均壓對來自該燒結步驟之該部件進行後處理步驟。
- 如請求項15至20中任一項之製造部件之 方法,其中,該黏合劑係選自由下列所形成之群組:聚乙二醇、乙酸丁酸纖維素、奈米纖維素、玉米澱粉、糖、聚乳酸、聚乙烯、聚丙烯、合成或天然蠟及硬脂酸。
- 一種由貴金屬硼化物形成之合金,該貴金屬選自包含下列之群組:金Au、銀Ag、鉑Pt、鈀Pd、釕Rh及銥Ir,該合金包含MxBy之結晶奈米粒子,其中M為貴金屬,貴金屬硼化物MxBy之結晶奈米粒子的y/x比係大於或等於1,該MxBy之結晶奈米粒子係分布於硼B之非晶形基質中或分布於B及貴金屬硼化物MzBa之非晶形基質中,其中z及a可分別等於或小於x及y。
- 如請求項23之合金,其中,該MxBy之結晶奈米粒子的y/x比係大於或等於2。
- 如請求項23之合金,其中,該貴金屬為金以及此為具有MxBy組成之18K金,其中,x等於1以及y接近6。
- 如請求項24之合金,其中,該貴金屬為金以及此為具有MxBy組成之18K金,其中,x等於1以及y接近6。
- 如請求項23之合金,其中,其含有其他合金化元素。
- 一種用於鐘錶之部件或用於首飾之部件,其係從如請求項23至27中任一項之合金製成。
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| EP19187108.6 | 2019-07-18 | ||
| EP19187108.6A EP3766997A1 (fr) | 2019-07-18 | 2019-07-18 | Procédé de fabrication d'alliages de métaux précieux et alliages de métaux précieux ainsi obtenus |
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| TWI750667B true TWI750667B (zh) | 2021-12-21 |
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| EP (3) | EP3766997A1 (zh) |
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| KR (2) | KR20210010978A (zh) |
| CN (2) | CN112239820A (zh) |
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| WO (1) | WO2021009349A1 (zh) |
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| EP4293430A1 (fr) | 2022-06-15 | 2023-12-20 | Manufacture d'Horlogerie Audemars Piguet SA | Procédé pour la fabrication d'une pièce à base de plusieurs métaux précieux et pièce résultante |
| EP4389319A1 (fr) | 2022-12-20 | 2024-06-26 | Manufacture d'Horlogerie Audemars Piguet SA | Procédé pour la fabrication d'un composant horloger à base d'alliage d'or et pièce résultante |
| CN116786837B (zh) * | 2023-04-14 | 2025-08-05 | 新疆大学 | 一种非煅烧制备Ni3B/Ni电催化剂的方法及应用 |
| WO2025224294A1 (fr) * | 2024-04-26 | 2025-10-30 | Patek Philippe Sa Geneve | Procede de fabrication d'un composant horloger ou de bijouterie et ledit composant horloger ou de bijouterie |
| WO2025224292A1 (fr) * | 2024-04-26 | 2025-10-30 | Patek Philippe Sa Geneve | Procede de fabrication d'un composant horloger ou de bijouterie et ledit composant horloger ou de bijouterie |
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| US6764561B1 (en) * | 2000-05-19 | 2004-07-20 | The United States Of America As Represented By The Secretary Of The Navy | Palladium-boron alloys and methods for making and using such alloys |
| TW200641157A (en) * | 2005-04-19 | 2006-12-01 | Stern Leach Company | Method for adding boron to metal alloys |
| US20120046482A1 (en) * | 2010-08-23 | 2012-02-23 | Hon Hai Precision Industry Co., Ltd. | Method for synthesizing gold nanoparticles |
| TW201250058A (en) * | 2011-02-16 | 2012-12-16 | Target Technology International Ltd | Methods of making and using palladium alloys |
| US8613788B2 (en) * | 2009-06-29 | 2013-12-24 | Heraeus Materials Technology Gmbh & Co. Kg | Increasing the strength of iridium, rhodium, and alloys thereof |
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| JPH02254101A (ja) * | 1989-03-28 | 1990-10-12 | Tanaka Kikinzoku Kogyo Kk | 合金微粉末の製造方法 |
| JP2749863B2 (ja) * | 1989-04-19 | 1998-05-13 | 田中貴金属工業株式会社 | 貴金属微粒子の調製方法 |
| US20060260778A1 (en) * | 2005-05-19 | 2006-11-23 | Stern Leach Company, A Corporation Of The State Of Delaware | Method for adding boron to metal alloys |
| CN101437967A (zh) * | 2005-04-19 | 2009-05-20 | 斯特恩利奇公司 | 向金属合金中加入硼的方法 |
| AU2008357012A1 (en) * | 2008-05-28 | 2009-12-03 | Aida Chemical Industries Co., Ltd. | Composition for precious metal sintering, process for producing precious metal sinter and precious metal sinter |
| EP2971198B1 (de) * | 2014-02-11 | 2016-10-05 | C. Hafner GmbH + Co. KG | Edelmetall-legierung zur verwendung in der schmuck- und uhrenindustrie |
| KR20160001514A (ko) * | 2014-06-27 | 2016-01-06 | 삼성전자주식회사 | 전도성 박막 |
| WO2015193515A1 (de) * | 2014-11-10 | 2015-12-23 | Heraeus Deutschland GmbH & Co. KG | Verfahren zur aufarbeitung edelmetall-haltiger materialien |
| JP6504321B2 (ja) * | 2017-03-28 | 2019-04-24 | 宇部興産株式会社 | 金属複合粒子の製造方法、金属複合粒子担持体の製造方法、及び粒子組成物 |
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- 2019-07-18 EP EP19187108.6A patent/EP3766997A1/fr not_active Withdrawn
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- 2020-05-20 TW TW109116692A patent/TWI750667B/zh active
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- 2020-06-11 EP EP20179530.9A patent/EP3766998A1/fr not_active Withdrawn
- 2020-06-19 KR KR1020200075003A patent/KR20210010978A/ko not_active Ceased
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- 2020-07-17 JP JP2021512706A patent/JP7252321B2/ja active Active
- 2020-07-17 WO PCT/EP2020/070283 patent/WO2021009349A1/fr not_active Ceased
- 2020-07-17 EP EP20739720.9A patent/EP3833791A1/fr active Pending
- 2020-07-17 US US17/273,918 patent/US11987869B2/en active Active
- 2020-07-17 KR KR1020217007618A patent/KR102494184B1/ko active Active
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| US6764561B1 (en) * | 2000-05-19 | 2004-07-20 | The United States Of America As Represented By The Secretary Of The Navy | Palladium-boron alloys and methods for making and using such alloys |
| TW200641157A (en) * | 2005-04-19 | 2006-12-01 | Stern Leach Company | Method for adding boron to metal alloys |
| US8613788B2 (en) * | 2009-06-29 | 2013-12-24 | Heraeus Materials Technology Gmbh & Co. Kg | Increasing the strength of iridium, rhodium, and alloys thereof |
| US20120046482A1 (en) * | 2010-08-23 | 2012-02-23 | Hon Hai Precision Industry Co., Ltd. | Method for synthesizing gold nanoparticles |
| TW201250058A (en) * | 2011-02-16 | 2012-12-16 | Target Technology International Ltd | Methods of making and using palladium alloys |
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| Publication number | Publication date |
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| JP2022501496A (ja) | 2022-01-06 |
| TW202106882A (zh) | 2021-02-16 |
| EP3766997A1 (fr) | 2021-01-20 |
| US20210331241A1 (en) | 2021-10-28 |
| KR102494184B1 (ko) | 2023-02-01 |
| KR20210010978A (ko) | 2021-01-29 |
| CN112771186B (zh) | 2022-04-19 |
| US11987869B2 (en) | 2024-05-21 |
| CN112771186A (zh) | 2021-05-07 |
| WO2021009349A1 (fr) | 2021-01-21 |
| JP2021017394A (ja) | 2021-02-15 |
| US20210017032A1 (en) | 2021-01-21 |
| CN112239820A (zh) | 2021-01-19 |
| KR20210044834A (ko) | 2021-04-23 |
| EP3833791A1 (fr) | 2021-06-16 |
| EP3766998A1 (fr) | 2021-01-20 |
| JP7252321B2 (ja) | 2023-04-04 |
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