TWI617533B - 表面改質陶瓷粉體及其應用 - Google Patents
表面改質陶瓷粉體及其應用 Download PDFInfo
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- TWI617533B TWI617533B TW105140857A TW105140857A TWI617533B TW I617533 B TWI617533 B TW I617533B TW 105140857 A TW105140857 A TW 105140857A TW 105140857 A TW105140857 A TW 105140857A TW I617533 B TWI617533 B TW I617533B
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- ceramic
- metal
- powder
- particles
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- 239000000843 powder Substances 0.000 title claims abstract description 229
- 239000000919 ceramic Substances 0.000 title claims abstract description 206
- 229910052751 metal Inorganic materials 0.000 claims abstract description 116
- 239000002184 metal Substances 0.000 claims abstract description 116
- 239000002245 particle Substances 0.000 claims abstract description 95
- 239000000463 material Substances 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 32
- 239000002105 nanoparticle Substances 0.000 claims description 28
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 239000002923 metal particle Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 7
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005313 bioactive glass Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 3
- 239000010931 gold Substances 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002156 mixing Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- -1 HA) Chemical compound 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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Abstract
一種表面改質陶瓷粉體,包括:複數個陶瓷顆粒以及至少部分包覆於每一個陶瓷顆粒之表面的表面改質材料。其中,陶瓷顆粒的平均粒徑實質介於10微米(μm)至100微米之間。表面改質材料係金屬、金屬氧化物或上述之組合。
Description
本說明書所揭露的是關於一種陶瓷粉體;特別是一種具有改質表面的陶瓷粉體,以及其應用。
雷射積層製造(AM,Additive Manufacturing)技術,是先將欲加工物件的立體圖結構區分成一層一層的平面結構。再利用聚焦雷射光束對包含有金屬粉體的材料粉末進行燒結,藉由不斷地重複鋪粉與雷射燒結動作,將每一層平面結構逐層堆疊起來,而製成所設計的加工物件。由於具有客製化、迅速、彈性及高價效比的優點,目前已廣泛應用於汽車、航太、模具、醫材、珠寶、藝術及民生消費產品等領域。
典型的積層製造過程中所使用的材料粉體,需要很高的流動性(flowability),使每一層粉體舖粉相對均勻,方可維持積層製造產品的品質。例如一般粉體流動率(powder flow rate)必需小於60秒/50克。典型的積層製造材料粉體一般包含金屬粉
體。應用於不同範圍可能會在金屬粉體中摻雜其他材料,例如陶瓷粉末。然而,其他材料的添加常導至材料粉體的流動性大幅降低,造成積層製造過程產生的舖粉不均勻的現象,間接影響積層製造的製程良率及加工物件的成型品質。
因此,目前亟需提供一種新的的表面改質陶瓷粉體及其應用此表面改質陶瓷粉體所製成的複合粉體,以增進複合粉體粉體的流動性。
本說明書中的一實施例是在提供一種表面改質陶瓷粉體。此表面改質陶瓷粉體包括:複數個陶瓷顆粒以及至少部分包覆於每一個陶瓷顆粒之表面的表面改質材料。其中,陶瓷顆粒的平均粒徑實質介於10微米(μm)至100微米之間。表面改質材料係金屬、金屬氧化物或上述之組合。
本說明書中的另一實施例是提供一種金屬/陶瓷複合粉體。此金屬/陶瓷複合粉體包括如前所述之表面改質陶瓷粉體以及複數個金屬顆粒。表面改質陶瓷粉體佔金屬/陶瓷複合粉體的重量百分比實質介於1至10之間;金屬顆粒佔金屬/陶瓷複合粉體的重量百分比實質介於90至99之間,且金屬顆粒的平均粒徑實質介於10微米至100微米之間。
本說明書中的又一實施例是在提供一種金屬/陶瓷複合粉體的製作方法,此方法包括下述步驟:首先提供複數個平
均粒徑實質介於10微米至100微米之間的陶瓷顆粒。接著,進行表面改質處理,將表面改質材料至少部分包覆於每一個陶瓷顆粒的表面,其中表面改質材料係金屬、金屬氧化物或上述之組合。後續,將表面改質處理後的陶瓷顆粒與複數個金屬顆粒均勻混合。
根據上述,本說明書的實施例是揭露一種表面改質陶瓷粉體、應用此表面改質陶瓷粉體所製成的複合粉體及其製作方法。表面改質陶瓷粉體係藉由在具有特定粒徑尺寸之陶瓷顆粒的表面至少部分地包覆材質為金屬、金屬氧化物或上述之組合的表面改質材料來增進金屬/陶瓷複合粉體的流動性。
在本說明書的一些實施例中,由表面改質陶瓷粉體與金屬粉體混合所製成的金屬/陶瓷複合粉體,具有實質介於30秒/50克至60秒/50克之間的流動性。可於積層製造過程中提供相對均勻的舖粉層,防止後續所進行的粉末燒結步驟產生厚度不均一的問題,藉以維持積層製造產品的品質。
100‧‧‧表面改質陶瓷粉體
101‧‧‧陶瓷顆粒
101a‧‧‧陶瓷顆粒的表面
102‧‧‧金屬改質層
200‧‧‧金屬/陶瓷複合粉體
201‧‧‧金屬粉體
201a‧‧‧金屬顆粒
301、302、303、304‧‧‧條帶
400‧‧‧表面改質陶瓷粉體
402‧‧‧奈米粒子
500‧‧‧金屬/陶瓷複合粉體
501‧‧‧金屬粉體
501a‧‧‧金屬顆粒
601、602、603、604、605、606‧‧‧條帶
S11‧‧‧提供由複數個陶瓷顆粒所構成的陶瓷粉體
S12‧‧‧進行一表面改質處理,在每一個陶瓷顆粒的表面形成一個金屬改質層
S41‧‧‧提供由複數個陶瓷顆粒所構成的陶瓷粉體
S42‧‧‧進行一表面改質處理,使複數個奈米粒子吸附於每一個陶瓷顆粒的表面上
為了對本說明書之上述實施例及其他目的、特徵和優點能更明顯易懂,特舉數個較佳實施例,並配合所附圖式,作詳細說明如下:第1A圖係根據本說明書的一實施例所繪示的一種製作表面改質陶瓷粉體的方法流程圖;
第1B圖係根據本說明書的一實施例所提供的一種陶瓷顆粒的電子顯微影像;第1C圖係繪示使用第1A圖的方法所形成之表面改質陶瓷粉體的電子顯微影像;第1D圖係第1C圖之電子顯微影像的局部放大圖;第2圖係根據本說明書的一實施例所提供的一種金屬/陶瓷複合粉體的電子顯微影像;第3圖係根據本說明書的一些實施例和比較例所繪示的複合粉體流動性測試結果分析圖;第4A圖係根據本說明書的一實施例所繪示的一種製作表面改質陶瓷粉體的方法流程圖;第4B圖係繪示使用第4A圖的方法所形成之表面改質陶瓷粉體的電子顯微影像;第4C圖係第4B圖之電子顯微影像的局部放大圖;第5圖係根據本說明書的一實施例所提供的一種金屬/陶瓷複合粉體的電子顯微影像;以及第6圖係根據本說明書的一實施例所繪示的複合粉體流動性測試結果分析圖。
本說明書所揭露的實施例是有關於一種表面改質陶瓷粉體及其應用此表面改質陶瓷粉體所製成的複合粉體,可增進
金屬/陶瓷複合粉體的流動性。為讓本發明之上述目的、特徵和優點能更明顯易懂,特舉數個較佳實施例,並配合所附圖式詳細描述如下。
但必須注意的是,這些特定的實施案例與方法,並非用以限定本發明。本發明仍可採用其他特徵、元件、方法及參數來加以實施。較佳實施例的提出,僅係用以例示本發明的技術特徵,並非用以限定本發明的申請專利範圍。該技術領域中具有通常知識者,將可根據以下說明書的描述,在不脫離本發明的精神範圍內,作均等的修飾與變化。在不同實施例與圖式之中,相同的元件,將以相同的元件符號加以表示。
請參照第1A圖至第1D圖,第1A圖係根據本說明書的一實施例所繪示的一種製作表面改質陶瓷粉體100的方法流程圖;第1B圖係根據本說明書的一實施例所提供的一種陶瓷顆粒101的電子顯微影像;第1C圖係繪示使用第1A圖的方法所形成之表面改質陶瓷粉體100的電子顯微影像;第1D圖係第1C圖之電子顯微影像的局部放大圖。
製作表面改質陶瓷粉體100的方法包括下述步驟:首先進行步驟S11,提供由複數個陶瓷顆粒101所構成的陶瓷粉體(如第1B圖所繪示)。在本說明書的一些實施例之中,構成陶瓷顆粒101的材料可以是(但不以此為限)氫氧基磷灰石(hydroxyapatite,HA)、磷酸鈣(Ca3(PO4)2)、生醫玻璃(Bioactive glass,Si-Ca-Na-P-O組合)、二氧化鈦(TiO2)、氧化鋯(ZrO2)、二
氧化矽(SiO2)、氧化鋁(Al2O3)或上述材料之任意組合。且陶瓷顆粒101的平均粒徑實質介於10微米至100微米之間。在本實施例中,陶瓷顆粒101係由氫氧基磷灰石所構成,陶瓷顆粒101的平均粒徑實質20微米至60微米之間。
接著對陶瓷顆粒101進行一個表面改質處理,將一種表面改質材料全部或部分地包覆在每一個陶瓷顆粒101的表面101a上,形成如第1C圖所繪示的表面改質陶瓷粉體100。在本實施例中,表面改質可以包括一個金屬沉積製程,例如可以是(但不以此為限)物理氣相沉積(Physical vapor deposition,PVD)步驟、化學氣相沉積(Chemical Vapor Deposition,CVD)製程、電鍍(electrolytic deposition)製程、無電電鍍(electroless plating)、溶膠凝膠(Sol-gel)製程,藉以在每一個陶瓷顆粒101的表面101a形成一個金屬改質層102(如步驟S12所示)。
例如,在本實施例中,金屬改質層102係藉由無電鍍步驟所形成表面具有圖案或無圖案的金屬改質層,無電鍍又稱之為化學鍍(chemical plating)或催化電鍍(autocatalytic plating)。無電鍍是指於水溶液中之金屬離子,受到環境參數控制直接化學還原於待鍍物上。其製程步驟為:(1)敏化(SnCl2 and HCl)。(2)水洗、過濾。(3)活化(PdCl2 and HCl)。(4)水洗、過濾、烘乾(100C,6-8hr)。(5)無電鍍金屬析鍍(CoSO4+NaPO2H2+Na3C6H5O7+NH4Cl;PH=8~9,T=90℃,t=10~30min),由析鍍時間控制膜層厚度。
在本說明書的一些實施例中,金屬改質層102包含金屬氧化物,金屬改質層102的厚度實質介於10奈米(nm)至100奈米之間。金屬改質層102的片電阻實質介於104歐姆/單位面積(Ω/S)至1011歐姆/單位面積(Ω/S)之間。金屬改質層102可以完全地包覆每一個陶瓷顆粒101的表面101a;也可以僅部分覆該在每一個陶瓷顆粒101的表面101a上。。在本說明書的一些實施例中,金屬改質層102對每一個陶瓷顆粒101的表面積覆蓋率實質介於40%至99%之間。
例如,在本實施例中,金屬改質層102並未完全地包覆每一個陶瓷顆粒101的表面101a(如第1D圖所繪示)。其中,金屬改質層102對每一個陶瓷顆粒101的表面積覆蓋率實質為80%。金屬改質層102的厚度實質為100奈米。金屬改質層102的片電阻實質為104歐姆/單位面積。
若將前述方法所製成的表面改質陶瓷粉體100與至少一種粒徑實質介於10微米至100微米之間的金屬粉體201均勻混合,可製作成一種金屬/陶瓷複合粉體200。請參照第2圖,第2圖係根據本說明書的一實施例所提供的一種金屬/陶瓷複合粉體200的電子顯微影像。
在本說明書的一實施例中,金屬粉體201可以包含採用鈦(Ti)、鉭(Ta)、鐵(Fe)、鎂(Mg)等金屬及其合金或上述之任意材料組合所形成的複數個金屬合金顆粒201a。其中,表面改質陶瓷粉體100佔該金屬/陶瓷複合粉體200的重量百分比,實
質介於1至10之間。金屬粉體201佔該金屬/陶瓷複合粉體200的重量百分比,實質介於90至99之間。
例如在本實施例中,係採用鈦合金粉末(Ti-6Al-4V)與表面改質陶瓷粉體100均勻混合,來製作成一種金屬/陶瓷複合粉體200。其中,鈦合金粉末(Ti-6Al-4V)佔金屬/陶瓷複合粉體200的重量百分比,實質為97;表面改質陶瓷粉體100佔該金屬/陶瓷複合粉體200的重量百分比,實質為3。
若將金屬/陶瓷複合粉體200與單純採用未改質之陶瓷顆粒101和金屬粉體201混合製成的複合粉體(比較例)進行粉體流動性測試。可以發現,金屬/陶瓷複合粉體200具有遠高於比較例的粉體流動性。且值得注意的是,摻雜不同重量比例之表面改質陶瓷粉體100的金屬/陶瓷複合粉體200,其粉體流動性也會有所不同。
例如請參照第3圖,第3圖係根據本說明書的一些實施例和比較例所繪示的複合粉體流動性測試結果分析圖。其中,條帶301和302分別代表包含有重量百分比5和1之表面改質陶瓷粉體100和重量百分比95和99之金屬粉體201混合所製成之金屬/陶瓷複合粉體200(即實施例1和2)的粉體流動率。條帶303和304分別代表包含有重量百分比5和1之未改質陶瓷顆粒與金屬粉體201和重量百分比95和99之金屬粉體201混合所製成之複合粉體(比較例1和2)的粉體流動率。條帶305和306分別代表包含有重量百分比5和1之未改質陶瓷顆粒、重量百分
比5和1之鈷粉體以及和重量百分比90和98之金屬粉體201混合所製成之複合粉體(比較例3和4)的粉體流動率。
由第3圖的測試結果可以發現,實施例1和2中採用本說明書實施例所提供之改質陶瓷粉體100所製成的金屬/陶瓷複合粉體200,其粉體流動率分別為57秒/50克和38.3秒/50克。比較例1和2所提供之複合粉體的粉體流動率皆大於90秒/50克;比較例3和4所提供之複合粉體的粉體流動率皆大於120秒/50克。比較例1、2、3和4所提供之複合粉體的粉體流動率數值遠大於實施例1和2所提供之金屬/陶瓷複合粉體200的粉體流動率(皆小於90秒/50克)。顯示,採用本說明書實施例所提供之改質陶瓷粉體100所製成的金屬/陶瓷複合粉體200,具有較佳的粉體流動性。而在本說明書的實施例1和2之中,又以包含有重量百分比1之表面改質陶瓷粉體100的金屬/陶瓷複合粉體200具有較佳的粉體流動性。
另外,在金屬/陶瓷複合粉體200中,金屬改質層102對每一顆陶瓷顆粒101表面的平均表面積覆蓋率也會影響金屬/陶瓷複合粉體200的粉體流動率。在本說明書的一實施例中,當金屬改質層102對每一顆陶瓷顆粒101表面的平均表面積覆蓋率實質為80%時,金屬/陶瓷複合粉體200的粉體流動率實質為57秒/50克。顯示,在混合金屬粉體201之前,對陶瓷顆粒101進行改質處理,可有效改善金屬/陶瓷複合粉體200的流動性。
請參照第4A圖至第4C圖,第4A圖係根據本說明
書的一實施例所繪示的一種製作表面改質陶瓷粉體400的方法流程圖;第4B圖係繪示使用第4A圖的方法所形成之表面改質陶瓷粉體400的電子顯微影像;第4C圖係第4B圖之電子顯微影像的局部放大圖。
製作表面改質陶瓷粉體400的方法包括下述步驟:首先進行步驟S41,提供由複數個陶瓷顆粒101所構成的陶瓷粉體(如第1B圖所繪示)。在本說明書的一些實施例之中,構成陶瓷顆粒101的材料可以是(但不以此為限)氫氧基磷灰石、磷酸鈣、生醫玻璃、二氧化鈦、氧化鋯、二氧化矽、氧化鋁或上述材料之任意組合。且陶瓷顆粒101的平均粒徑實質介於10微米至100微米之間。在本實施例中,陶瓷顆粒101係由氫氧基磷灰石所構成,陶瓷顆粒101的平均粒徑實質20微米至60微米之間。
接著,對至少一個陶瓷顆粒101進行一個表面改質處理,將一種表面改質材料全部或部分地包覆在陶瓷顆粒101的表面101a上,形成如第4B圖所繪示的表面改質陶瓷粉體400。在本實施例中,表面改質處理包括一個奈米粒子吸附製程,使複數個奈米粒子402藉由靜電作用吸附於陶瓷顆粒101的表面101a上(如步驟S42所示)。在本說明書的一些實施例中,表面改質陶瓷粉體400的每一個陶瓷顆粒101的表面101a都吸附有複數個奈米粒子402。但在本說明書的另一些實施例中,表面改質陶瓷粉體400中只有一部分陶瓷顆粒101的表面101a吸附有複數個奈米粒子402,另一部分陶瓷顆粒101的表面101a並未吸附有複數個
奈米粒子402。
在本說明書的一些實施例之中,構成該些奈米粒子402的材料,可以是(但不以此為限)二氧化鈦、氧化鋁、氧化鋯或上述材料之任意組合。這些奈米粒子402的平均粒徑實質介於10奈米至100奈米之間。奈米粒子402可以完全地包覆每一個陶瓷顆粒101的表面101a,也可以僅部分地覆蓋於每一個陶瓷顆粒101的表面101a上。奈米粒子402與這些陶瓷顆粒101的整體重量之比值,實質介於1%至50%之間,在本說明書的一些實施例之中,奈米粒子402與這些陶瓷顆粒101的整體重量之比值實質介於1/10至5/10之間。
例如,在本實施例中,奈米粒子402並未完全地包覆每一個陶瓷顆粒101的表面101a(如第4C圖所繪示)。其中,奈米粒子402對每一個陶瓷顆粒101的表面積覆蓋率實質介於40%至99%。奈米粒子402與這些陶瓷顆粒101的整體重量之比值實質為3/10。
若將前述方法所製成的表面改質陶瓷粉體400與至少一種粒徑實質介於10微米至100微米之間的金屬粉體501均勻混合,可製作成一種金屬/陶瓷複合粉體500。請參照第5圖,第5圖係根據本說明書的一實施例所提供的一種金屬/陶瓷複合粉體500的電子顯微影像。
在本說明書的一實施例中,金屬粉體501可以包含採用,例如鈦、鉭、鐵、鎂金屬及其合金或上述材料之任意組合,
所形成的複數個金屬顆粒501a。其中,表面改質陶瓷粉體400佔該金屬/陶瓷複合粉體500的重量百分比,實質介於1至10之間。金屬粉體501佔金屬/陶瓷複合粉體500的重量百分比,實質介於90至99之間。
例如在本實施例中,係採用鈦合金粉末(Ti-6Al-4V)與表面改質陶瓷粉體400均勻混合,來製作成一種金屬/陶瓷複合粉體500。其中,鈦合金粉末(Ti-6Al-4V)佔金屬/陶瓷複合粉體500的重量百分比,實質為97;表面改質陶瓷粉體400佔該金屬/陶瓷複合粉體500的重量百分比,實質為3。
若將金屬/陶瓷複合粉體500與單純採用未改質之陶瓷顆粒101和金屬粉體501混合製成的複合粉體(比較例)進行粉體流動性測試。可以發現,金屬/陶瓷複合粉體500具有遠高於比較例的粉體流動性。且值得注意的是,摻雜不同重量比例之表面改質陶瓷粉體400的金屬/陶瓷複合粉體500,其粉體流動性也會有所不同。
例如請參照第6圖,第6圖係根據本說明書的一些實施例和比較例所繪示的複合粉體流動性測試結果分析圖。其中,條帶601至603分別代表摻雜有重量百分比5、3和1之表面改質陶瓷粉體400和重量百分比95、97和99之金屬粉體501混合所製成之金屬/陶瓷複合粉體500(即實施例3、4和5)的粉體流動率。條帶604至606分別代表包含有重量百分比5、3和1之未改質陶瓷顆粒101與金屬粉體501和重量百分比95、97和
99之金屬粉體201混合所製成混合所製成之複合粉體(比較例5、6和7)的粉體流動率。條帶607至608分別代表包含有重量百分比5和1之未改質陶瓷顆粒101和奈米粒子402以及重量百分比95和99之金屬粉體201三者同時混合,所製成混合所製成之複合粉體(比較例8和9)的粉體流動率。
由第6圖的測試結果可以發現,實施例3、4和5中採用本說明書實施例所提供之改質陶瓷粉體400所製成的金屬/陶瓷複合粉體500,其粉體流動率分別為40.58秒/50克、36.32秒/50克和35.66秒/50克。比較例5、6和7所提供之複合粉體的粉體流動率皆大於90秒/50克,遠大於實施例3、4和5所提供之金屬/陶瓷複合粉體500的粉體流動率(皆小於40秒/50克)。比較例8和9所提供之複合粉體的粉體流動率分別為75.2秒/50克和57.2秒/50。與未添加奈米粒子402的比較例5、6和7相比,流動率雖有改善,但仍比實施例3和5的效果差。
顯示採用本說明書之實施例所提供之表面改質陶瓷粉體400所製成的金屬/陶瓷複合粉體500具有較佳的粉體流動性。即便是採用了奈米粒子402來與未改質陶瓷顆粒101、奈米粒子402以及金屬粉體201三者同時混合(例如比較例8和9),若在混合金屬粉體201之前,未對陶瓷顆粒101進行改質處理,未改質陶瓷顆粒101、奈米粒子402以及金屬粉體201三者同時混合所製成之複合粉體(比較例8和9)的粉體流動率,仍只有本說明書之實施例3和5所提供之金屬/陶瓷複合粉體500之粉體流動率
的約一半左右。而在本說明書的實施例3、4和5之中,又以摻雜有重量百分比1之表面改質陶瓷粉體100的金屬/陶瓷複合粉體500具有較佳的粉體流動性。
同樣的,在金屬/陶瓷複合粉體500中,奈米粒子402對每一顆陶瓷顆粒101表面的平均表面積覆蓋率也會影響金屬/陶瓷複合粉體500的粉體流動率。在本說明書的一實施例中,當奈米粒子402對每一顆陶瓷顆粒101表面的平均表面積覆蓋率實質為40%時,金屬/陶瓷複合粉體500的粉體流動率實質為45秒/50克。當奈米粒子402對每一顆陶瓷顆粒101表面的平均表面積覆蓋率實質為99%時,金屬/陶瓷複合粉體500的粉體流動率實質為35秒/50克。顯示,在混合金屬粉體201之前,對陶瓷顆粒101進行改質處理,可有效改善金屬/陶瓷複合粉體500的流動性。
根據上述,本說明書的實施例是揭露一種表面改質陶瓷粉體、應用此表面改質陶瓷粉體所製成的複合粉體及其製作方法。表面改質陶瓷粉體係藉由在具有特定粒徑尺寸之陶瓷顆粒的表面至少部分地包覆材質為金屬、金屬氧化物或上述之組合的表面改質材料來增進複合粉體粉體的流動性。
在本說明書的一些實施例中,由表面改質陶瓷粉體與金屬粉體混合所製成的金屬/陶瓷複合粉體,具有實質介於30秒/50克至60秒/50克之間的流動性。可於積層製造過程中提供相對均勻的舖粉層,防止後續所進行的粉末燒結步驟產生厚度不均一的問題,藉以維持積層製造產品的品質。
綜上所述,雖然本說明書已以較佳實施例揭露如上,然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者,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。
Claims (15)
- 一種表面改質陶瓷粉體,包括:複數個陶瓷顆粒,具有實質介於10微米(μm)至100微米之間的一平均粒徑;以及一表面改質材料,至少部分包覆於每一該些陶瓷顆粒的一表面,其中該表面改質材料係選自於由一金屬、一金屬氧化物及上述之組合所組成的一族群。
- 如申請專利範圍第1項所述之表面改質陶瓷粉體,其中該表面改質材料包括一金屬改質層,至少部分地覆蓋於每一該些陶瓷顆粒的該表面。
- 如申請專利範圍第2項所述之表面改質陶瓷粉體,其中該表面改質材料係選自於由鐵(Fe)、鈷(Co)、鈦(Ti)、鉭(Ta)、鈀(Pd)、銀(Ag)、金(Au)以及上述之任意組合所組成的一族群。
- 如申請專利範圍第2項所述之表面改質陶瓷粉體,其中該金屬改質層具有實質介於10奈米(nm)至100奈米之間的一厚度。
- 如申請專利範圍第2項所述之表面改質陶瓷粉體,其中該金屬改質層對每一該些陶瓷顆粒具有實質介於40%至99%之間的一表面積覆蓋率。
- 如申請專利範圍第1項所述之表面改質陶瓷粉體,其中該表面改質材料包括複數個奈米粒子,吸附於至少一該些陶瓷顆粒的該表面;且該些奈米粒子具有實質介於10奈米至100奈米之間的一平均粒徑。
- 如申請專利範圍第6項所述之表面改質陶瓷粉體,其中構成該些奈米粒子的材料包括一金屬氧化物,該金屬氧化物係二氧化鈦(TiO2)、氧化鋁(Al2O3)、氧化鋯(ZrO)或上述之任意組合。
- 如申請專利範圍第1項所述之表面改質陶瓷粉體,其中該表面改質材料與該些陶瓷顆粒具有實質介於1%至50%的一重量比。
- 如申請專利範圍第1項所述之表面改質陶瓷粉體,其中每一該些陶瓷顆粒包括一陶瓷材料,且該陶瓷材料係氫氧基磷灰石(hydroxyapatite,HA)、磷酸鈣(Ca3(PO4)2)、生醫玻璃(Bioactive glass,Si-Ca-Na-P-O)、二氧化鈦(TiO2)、氧化鋯(ZrO2)、二氧化矽(SiO2)、氧化鋁(Al2O3)或上述材料之任意組合。
- 一種金屬/陶瓷複合粉體,包括:如申請專利範圍第1至9項之一者所述之該表面改質陶瓷 粉體,佔該金屬/陶瓷複合粉體實質介於1至10之間的一重量百分比;以及複數個金屬顆粒,佔該金屬/陶瓷複合粉體實質介於90至99之間的一重量百分比,且該些金屬顆粒具有實質介於10微米至100微米之間的一平均粒徑。
- 如申請專利範圍第10項所述之金屬/陶瓷複合粉體,其中該些金屬顆粒包括一金屬材料,該金屬材料係選自於鈦、鉭、鐵、鎂以及上述之任意組合。
- 如申請專利範圍第10項所述之金屬/陶瓷複合粉體,具有實質介於30秒/50克至60秒/50克之間的一粉體流動率(powder flow rate)。
- 一種金屬/陶瓷複合粉體的製作方法,包括:提供複數個陶瓷顆粒,使其具有實質介於10微米至100微米之間的一平均粒徑;進行一表面改質處理,將一表面改質材料至少部分包覆於每一該些陶瓷顆粒的一表面,其中該表面改質材料係選自於由一金屬、一金屬氧化物及上述之組合所組成的一族群;以及將表面改質處理後之該些陶瓷顆粒與複數個金屬顆粒均勻混合。
- 如申請專利範圍第13項所述之陶瓷粉體的製作方法,其中該表面改質處理包括一金屬沉積製程,形成一金屬改質層至少部分覆蓋於每一該些陶瓷顆粒的該表面。
- 如申請專利範圍第13項所述之陶瓷粉體的製作方法,其中該表面改質處理包括一奈米粒子吸附製程,使複數個奈米粒子吸附於每一該些陶瓷顆粒的該表面上。
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CN108610059B (zh) | 2021-10-22 |
TW201821392A (zh) | 2018-06-16 |
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