本文選題：生物醫(yī)用鈦合金 + 制備工藝　； 參考：《湘潭大學(xué)》2015年博士論文

【摘要】：鈦合金由于具有良好的生物相容性、優(yōu)異的耐腐蝕性能和力學(xué)性能,作為生物移植材料有著廣闊的應(yīng)用前景,而與同成分的晶態(tài)合金相比,非晶態(tài)合金具有較低的彈性模量,較高的強(qiáng)度和優(yōu)異的耐磨耐蝕性能,因而作為生物醫(yī)用移植材料,有著潛在的應(yīng)用前景。然而,目前開發(fā)的鈦基非晶合金還存在兩個問題,限制了該非晶合金的實(shí)際應(yīng)用。其一,非晶形成能力較好的鈦基非晶合金中通常含有對人體有毒的元素,而不含有毒元素的鈦合金,其非晶形成能力較差,難于制備出尺寸較大的塊體非晶合金,其二,鈦基非晶合金在室溫下幾乎沒有塑性。因此,開發(fā)出不含對人體有害元素且具有一定非晶形成能力鈦基非晶合金,并制備成大塊,同時改善非晶合金的室溫塑性,是促進(jìn)鈦基非晶合金作為生物移植材料在實(shí)際應(yīng)用中的關(guān)鍵。為此,本文首先通過非晶合金形成的熱力學(xué)和動力學(xué)理論分析,設(shè)計(jì)出了兩種不含有毒元素的Ti-Zr-Ta-Si-Sn和Ti-Zr-Ta-Si-Nb非晶合金體系,并分別采用單輥甩帶法和水冷銅模吸鑄法制備了Ti-Zr-Ta-Si-Sn非晶合金薄帶和高強(qiáng)Ti-Zr-Ta-Si-Nb合金,研究了Sn元素和Nb元素對合金非晶形成能力及其耐蝕性能和力學(xué)性能的影響,在此基礎(chǔ)上,采用粉末冶金和高壓燒結(jié)的方法制備出了塊體鈦基非晶基及其復(fù)合材料,探討了制備工藝對Ti基非晶及其復(fù)合材料顯微組織、熱力學(xué)行為、力學(xué)行為的影響及其機(jī)理。論文創(chuàng)新性結(jié)論如下:1.開發(fā)了一種不含有毒元素的Ti-Zr-Ta-Si-Sn非晶合金,并采用甩帶法制備出了該非晶合金薄帶,研究了Sn元素對(Ti60Zr10Ta15Si15)100-x Snx(x=0,4,8 at.%)非晶合金的非晶形成能力、熱力學(xué)行為和腐蝕行為的影響。研究表明,采用甩帶法,可成功制備出(Ti60Zr10Ta15Si15)100-x Snx(x=0,4,8 at.%)非晶合金薄帶,隨著Sn的增加,合金的非晶形成能力略有下降;在該合金體系中加入Sn可促進(jìn)非晶合金表面致密的鈍化膜的形成,從而提高了合金的耐腐蝕性能;Sn的加入對該非晶合金的顯微硬度和彈性模量也會產(chǎn)生重要影響,分析結(jié)果表明,Sn的加入可改變該非晶合金體系的自由體積,從而影響非晶合金的力學(xué)性能。2.采用Nb部分替代Ti-Zr-Ta-Si非晶合金中的Ta元素,開發(fā)出Ti-Zr-Ta-Si-Nb系非晶合金體系,并采用水冷銅模吸鑄法制備出了Ti60Zr10Si15Ta15-x Nbx(x=0,3,7,11 at.%)合金。研究結(jié)果表明,雖然從理論分析上可知用Nb部分替代該非晶體系中的Ta有助于提高非晶合金的非晶形成能力并降低合金成本,但采用水冷銅模吸鑄法難于制備Ti60Zr10Si15Ta15-x Nbx(x=0,3,7,11 at.%)塊體非晶合金,對鑄態(tài)的合金顯微組織和力學(xué)性能分析測試結(jié)果表明,該合金由β-Ti及細(xì)小晶化相Ti2Zr、Ti Si、Si3Ti2Zr等相組成,其中Ti60Zr10Si15Ta8Nb7的斷裂強(qiáng)度高達(dá)2150 MPa;該合金在磷酸緩沖鹽溶液中表現(xiàn)出優(yōu)良的耐蝕性能,且隨著Nb含量的增加,其耐腐蝕性能增加,但其耐蝕性能低于非晶態(tài)的Ti60Zr10Ta15Si15。3.用機(jī)械球磨法制備了非晶態(tài)的Ti60Zr10Ta15Si15粉末,并采用高壓燒結(jié)法制備出了塊體Ti60Zr10Ta15Si15非晶合金。研究發(fā)現(xiàn),球磨工藝參數(shù)對Ti合金粉末非晶化效率有重大影響,當(dāng)球料比為20∶1,大小球的質(zhì)量比為1∶2時,轉(zhuǎn)速為350 rpm時,且分散劑占粉末質(zhì)量的0.2%時,球磨60 h,鈦合金粉末的非晶化效率最高;溫度、壓力對燒結(jié)材料的顯微組織和力學(xué)性能都有重要的影響,在過冷液相區(qū)內(nèi)(780 K)高壓燒結(jié)Ti60Zr10Ta15Si15合金,非晶未發(fā)生晶化。而在高于晶化溫度(820 K)下燒結(jié),非晶態(tài)合金發(fā)生了明顯的晶化。更高的燒結(jié)壓力(5 GPa)未導(dǎo)致粉末發(fā)生明顯的晶化,且使得材料的孔洞分布更均勻,組織更致密,彈性模量和斷裂強(qiáng)度分別得到提高。耐磨性能更好,維氏硬度更大。4.通過在鈦非晶粉末中添加純鈦粉,并采用高壓燒結(jié)的的方法制備出了鈦非晶基復(fù)合材料。結(jié)果表明,純鈦的體積分?jǐn)?shù)和燒結(jié)保壓時間對非晶復(fù)合材料的顯微組織和室溫壓縮性能具有重要的影響。在燒結(jié)過程中,混合物中沒有出現(xiàn)新的物相,燒結(jié)過程主要是非晶相和純鈦相的物理擴(kuò)散控制,復(fù)合材料具有一定的塑性;保壓時間對非晶復(fù)合材料的顯微結(jié)構(gòu)、顯微組織和室溫壓縮性能也具有重要的影響。對燒結(jié)材料的物相鑒定顯示,當(dāng)保壓時間從10 min增加到120 min,沒有新的相產(chǎn)生,且顆粒結(jié)合更緊密,導(dǎo)致復(fù)合材料力學(xué)性能更好。
[Abstract]:Titanium alloy has good biocompatibility, excellent corrosion resistance and mechanical properties, as biological graft material has broad application prospect, and amorphous alloy with the same composition as compared to amorphous alloy has a low elastic modulus, high strength and excellent abrasion resistance and corrosion resistance, so as a biomedical implant materials, has a potential application prospect. However, titanium based amorphous alloy is also the development of the two problems, limits the practical application of the amorphous alloy. On the one hand, the formation of amorphous Ti based amorphous alloy has good ability in general on the human body contains toxic elements, but does not contain toxic elements in titanium alloy the glass forming ability is poor, it is difficult to fabricate large bulk amorphous alloy, the titanium based amorphous alloy at room temperature almost no plastic. Therefore, the development of free of harmful elements and has a certain The forming ability of amorphous Ti based amorphous alloy, and prepared into blocks, while improving the ductility of amorphous alloys, Ti based amorphous alloy is promoted as a key biological graft material in practical application. Therefore, this paper through the thermodynamics and kinetics of amorphous alloy formation theory analysis, design and Ti-Zr-Ta-Si-Sn Ti-Zr-Ta-Si-Nb two does not contain toxic elements of the amorphous alloy system, and adopts single spinning and water-cooled copper mold suction casting method to prepare Ti-Zr-Ta-Si-Sn amorphous alloy ribbons and high-strength Ti-Zr-Ta-Si-Nb alloy, to study the Sn element and the Nb element of amorphous alloy formation and corrosion resistance and mechanical properties of this. Based on the prepared block based and titanium based Amorphous Composites by powder metallurgy method and high-pressure sintering system, discusses on the microstructure of Ti amorphous alloys and their composites prepared by thermal. The behavior, influence the mechanical behavior and its mechanism. The innovation of this paper are as follows: 1. the development of a does not contain toxic elements of Ti-Zr-Ta-Si-Sn amorphous alloy, and the ribbon was prepared by the amorphous alloy ribbons of Sn elements on 100-x Snx (Ti60Zr10Ta15Si15) (x= 0,4,8 at.%) amorphous formation the ability of amorphous alloy, thermal behavior and corrosion behavior. The results show that the melt spinning method, can be successfully prepared (Ti60Zr10Ta15Si15) 100-x Snx (x=0,4,8 at.%) amorphous alloy ribbon, with the increase of Sn amorphous alloy forming ability decreased slightly; adding Sn can promote the formation of passive film the surface density of the amorphous alloy in this alloy system, thereby improving the corrosion resistance of alloy; adding micro hardness and elastic modulus of the amorphous alloy Sn would also influence the analysis results show that the addition of Sn can change the amorphous The free volume of gold system, thus affecting the mechanical properties of.2. amorphous alloys by partial substitution of Nb Ti-Zr-Ta-Si non Ta amorphous alloy elements in the development of Ti-Zr-Ta-Si-Nb amorphous alloy system, and the use of water-cooled copper mold suction casting was prepared by Ti60Zr10Si15Ta15-x Nbx (x=0,3,7,11 at.%) alloys. The results show that although in theory we use Nb to replace part of the amorphous Ta system helps to improve the glass forming ability of amorphous alloy alloy and reduce the cost, but by the water-cooled copper mold suction casting method to prepare Ti60Zr10Si15Ta15-x Nbx (x=0,3,7,11 at.%) bulk amorphous alloy, according to the analysis of microstructure of as cast alloy and mechanical performance test the result, the alloy is composed of beta -Ti and fine crystalline phase Ti2Zr, Ti Si, Si3Ti2Zr and other phases, the fracture strength of Ti60Zr10Si15Ta8Nb7 is up to 2150 MPa; the alloy in phosphate buffer salt solution table The excellent corrosion resistance, and with the increase of Nb content, the corrosion resistance increased, but its corrosion resistance is lower than that of the amorphous Ti60Zr10Ta15Si15.3. Ti60Zr10Ta15Si15 was prepared by mechanical ball milling powder is amorphous, and the high pressure sintering prepared bulk amorphous Ti60Zr10Ta15Si15 alloy. The study found that milling process parameters on Ti the efficiency of amorphous alloy powder has a significant effect, when the ball material ratio is 20: 1, quality of the size of the ball is 1: 2, the speed is 350 rpm, and accounted for 0.2% of the mass of powder dispersing agent, 60 h of milling titanium alloy powder, the highest amorphization efficiency; temperature are important effect of pressure on the microstructure and mechanical properties of sintered materials, in the supercooled liquid region (780 K) Ti60Zr10Ta15Si15 amorphous alloy high pressure sintering, not crystallize. In higher crystallization temperature (820 K) under the sintering of amorphous alloy has obvious The crystallization. The sintering pressure higher (5 GPa) did not cause obvious crystallization of powder, and makes the hole material distribution is more uniform, more compact structure, elastic modulus and fracture strength were improved. The better wear resistance, hardness of Vivtorinox greater.4. by adding titanium in titanium powder and amorphous powder. The system of the high pressure sintering method prepared Ti amorphous matrix composites. The results showed that the volume fraction of pure titanium and sintering has important influence on the microstructure pressure on Amorphous Composites and compressive properties at room temperature. During the sintering process, the mixture do not appear in the new phase, the sintering process is mainly amorphous and pure titanium physical diffusion control, composite material has certain plasticity; holding time on Microstructure of Amorphous Composites, microstructure and compressive properties at room temperature also has an important effect on the sintering material phase. The identification shows that when the holding time increases from 10 min to 120 min, there is no new phase, and the combination of particles is more compact, which leads to better mechanical properties of the composite.

【學(xué)位授予單位】：湘潭大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TG139.8;TB33

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