【摘要】：超高分子量聚乙烯(ultra-high molecular weight polyethylene,UHMWPE)化學(xué)結(jié)構(gòu)簡單、生物相容性突出、耐腐蝕、耐磨損,綜合性能優(yōu)異,被廣泛應(yīng)用于醫(yī)療、漁業(yè)、防護(hù)、工程等領(lǐng)域。UHMWPE也存在一些性能不足,比如表面能低、抗蠕變性差、耐溫性低,此外耐磨性也有待提高,這限制了其在復(fù)合材料、工程領(lǐng)域的部分應(yīng)用。因此,通過化學(xué)或物理方法改善其表面性質(zhì)、提高抗蠕變性及耐磨性具有重要意義。輻射改性是一種有效改變高分子材料性能的方法,為此本論文以UHMWPE輻射效應(yīng)為立足點(diǎn),詳細(xì)研究了UHMWPE的輻射氧化、接枝和交聯(lián),利用輻射氧化或輻射接枝提高UHMWPE表面潤濕性,利用輻射交聯(lián)提高UHMWPE抗蠕變性和耐磨性,另外借助共混輻射改性多壁碳納米管(MWCNTs)改善了UHMWPE的力學(xué)性能。具體研究內(nèi)容及結(jié)果如下:(1)、UHMWPE粉末的輻射氧化采用γ射線和電子束(EB)在空氣中對UHMWPE粉末樣品進(jìn)行輻照,詳細(xì)研究了粉末接受射線輻照后化學(xué)結(jié)構(gòu)、潤濕性和熱穩(wěn)定性變化情況,比較了吸收劑量和劑量率對材料結(jié)構(gòu)、性質(zhì)變化的影響并對氧化裂解程度進(jìn)行計(jì)算。結(jié)果表明:UHMWPE粉末在空氣中受γ射線/EB輻照后,裂解占主導(dǎo)地位;吸收劑量和劑量率對氧化裂解程度有顯著影響。在低劑量率、高劑量條件下輻射氧化裂解更為嚴(yán)重,γ射線輻照300 kGy的樣品可氧化裂解完全;此外,低劑量率輻照引發(fā)的氧化裂解程度可根據(jù)氧氣擴(kuò)散速度與劑量率進(jìn)行估算。雖然UHMWPE粉末受到高劑量輻照后氧化裂解嚴(yán)重,但其熱穩(wěn)定性、潤濕性變化較小。單純輻射氧化對UHMWPE表面性質(zhì)影響不大。(2)、UHMWPE粉末/薄膜預(yù)輻射接枝丙烯酸(AA)采用預(yù)輻射接枝方法,將γ射線輻照的UHMWPE粉末/薄膜在1 wt%AA溶液中進(jìn)行反應(yīng),接枝少量AA以改善其親水性。詳細(xì)研究了UHMWPE粉末/薄膜受γ射線輻照、接枝AA、氫氧化鈉(NaOH)中和處理后化學(xué)結(jié)構(gòu)、表面潤濕性變化情況。結(jié)果表明:UHMWPE粉末/薄膜表面成功接枝了AA,且粉末樣品更有利于接枝反應(yīng)進(jìn)行,接枝少量AA后樣品表面潤濕性明顯提高,中和處理進(jìn)一步提高了潤濕性。接枝6 wt%AA的粉末樣品,用NaOH中和處理后可在水溶液中分散,表現(xiàn)出良好的親水性。最終,通過接枝少量AA的方式制備了親水性UHMWPE粉末。(3)、交聯(lián)UHMWPE片材蠕變行為研究采用γ射線輻照和真空退火方式制備了交聯(lián)的UHMWPE片材,詳細(xì)研究了片材交聯(lián)后凝膠含量、結(jié)晶度、蠕變和力學(xué)性能的變化。結(jié)果表明:UHMWPE片材輻射交聯(lián)后凝膠含量、結(jié)晶度增加,抗蠕變性大幅提高,力學(xué)性能亦明顯改善;300 kGy輻射交聯(lián)的UHMWPE片材在270°C、0.06 MPa條件下拉伸4 h后依舊保持良好形貌,其楊氏模量亦由原始UHMWPE片材接近400 MPa增加到1400 MPa,增加幅度接近250%。此外,退火處理增加交聯(lián)有利于片材抗蠕變性和模量提高。最終,通過輻射交聯(lián)制備了具有良好抗蠕變性的UHMWPE板材。(4)、UHMWPE/X-UHMWPE復(fù)合材料摩擦行為研究采用輻射交聯(lián)和共混方法將交聯(lián)UHMWPE(X-UHMWPE)添加到常規(guī)UHMWPE中制備復(fù)合材料,詳細(xì)研究了X-UHMWPE本身性質(zhì)及復(fù)合材料摩擦行為。結(jié)果表明:UHMWPE粉末輻射交聯(lián)后加工性能下降,高劑量輻照的樣品難以熔融;在UHMWPE中添加少量X-UHMWPE使復(fù)合材料綜合性能大幅改善,耐磨性大幅提高并保持較好延展性。如添加25 wt%150 kGy輻射交聯(lián)的X-UHMWPE到常規(guī)UHMWPE中制備的復(fù)合材料,相對于原始UHMWPE而言,其耐磨性提高130%并保持90%的拉伸強(qiáng)度和70%的延展性。(5)、UHMWPE/MWCNTs復(fù)合材料力學(xué)行為研究采用γ射線輻照和共混方式將原始及經(jīng)γ射線輻照(60 kGy)的MWCNTs添加到UHMWPE中制備復(fù)合材料,詳細(xì)研究了MWCNTs經(jīng)γ射線輻照(60 kGy)后結(jié)構(gòu)及復(fù)合材料力學(xué)性能的變化。結(jié)果表明:MWCNTs經(jīng)γ射線輻照后表面化學(xué)結(jié)構(gòu)發(fā)生變化、缺陷增加但形貌變化微小;添加少量輻射改性的MWCNTs可有效提升復(fù)合材料力學(xué)性能,如添加2 wt%γ射線輻射改性的MWCNTs可提高20%的屈服強(qiáng)度;但引入少量MWCNTs難以有效提升復(fù)合材料的導(dǎo)熱性質(zhì)。
[Abstract]:The ultra-high molecular weight polyethylene (UHMWPE) has the advantages of simple chemical structure, outstanding biocompatibility, corrosion resistance, abrasion resistance and comprehensive performance, and is widely applied to the fields of medical treatment, fishery, protection, engineering and the like. The UHMWPE also has some poor properties, such as low surface energy, poor creep resistance, low temperature resistance, and increased wear resistance, which limits its application in the composite and engineering fields. Therefore, it is of great significance to improve the surface properties, improve the creep resistance and wear resistance by the chemical or physical method. The radiation modification is a method for effectively changing the properties of the high-molecular material. In this paper, the radiation oxidation, grafting and cross-linking of UHMWPE are studied in detail by the radiation effect of UHMWPE, and the wettability of the surface of the UHMWPE is improved by radiation oxidation or radiation grafting. The anti-creep and wear resistance of UHMWPE were improved by radiation cross-linking, and the mechanical properties of UHMWPE were improved by co-mixed radiation-modified multi-wall carbon nanotubes (MWCNTs). The specific research contents and results are as follows: (1) The radiation oxidation of UHMWPE powder is irradiated by X-ray and electron beam (EB) in air, and the chemical structure, wettability and thermal stability of the powder after radiation irradiation are studied in detail. The effect of absorbed dose and dose rate on the structure and properties of the material was compared, and the degree of oxidative cracking was calculated. The results show that the degradation of UHMWPE powder in air is dominated by X-ray/ EB irradiation, and the absorbed dose and dose rate have a significant effect on the degree of oxidative cleavage. In addition, the degree of oxidative cracking induced by low dose rate irradiation can be estimated according to the rate of oxygen diffusion and dose rate. Although the UHMWPE powder is subjected to high-dose irradiation, the oxidative cracking is severe, but the thermal stability and the wettability change are small. The effect of simple radiation oxidation on the surface properties of UHMWPE is not great. (2) The UHMWPE powder/ film pre-radiation grafted acrylic acid (AA) was grafted with a pre-radiation grafting method, and the X-ray irradiated UHMWPE powder/ film was reacted in a 1 wt% AA solution, and a small amount of AA was grafted to improve its hydrophilicity. The chemical structure and surface wettability of UHMWPE powder/ film under X-ray irradiation, grafting AA, sodium hydroxide (NaOH) and post-treatment were studied in detail. The results show that the surface of UHMWPE powder/ film is grafted with AA, and the powder sample is more beneficial to the grafting reaction, and the surface wettability of the sample after the grafting of a small amount of AA is obviously improved, and the wettability is further improved in the neutralization treatment. The powder sample of 6 wt% AA was grafted and dispersed in an aqueous solution after neutralization with NaOH to show good hydrophilicity. Finally, a hydrophilic UHMWPE powder was prepared by grafting a small amount of AA. (3) The cross-linked UHMWPE sheet was prepared by X-ray irradiation and vacuum annealing, and the changes of gel content, crystallinity, creep and mechanical properties of the cross-linked UHMWPE were studied in detail. The results show that the gel content, crystallinity, creep resistance and mechanical properties of UHMWPE sheet after radiation cross-linking are improved greatly, and the mechanical properties are improved obviously. The 300 kGy radiation cross-linked UHMWPE sheet is still in good shape after being stretched for 4 h under the condition of 270 擄 C and 0. 06MPa. The Young's modulus is also increased to 1400 MPa from the original UHMWPE sheet to 1400 MPa, and the increase is close to 250%. in addition, that increase of the degree of cross-linking of the anneal treatment facilitates the creep and modulus of the sheet. Finally, UHMWPE plates with good creep resistance were prepared by radiation crosslinking. (4) The friction behavior of UHMWPE/ X-UHMWPE composites was investigated by radiation cross-linking and blending. The composite materials were prepared by adding cross-linked UHMWPE (X-UHMWPE) to conventional UHMWPE, and the properties of the X-UHMWPE and the friction behavior of the composites were studied in detail. The results show that after the radiation cross-linking of UHMWPE powder, the processing property is decreased, and the sample with high dose irradiation is difficult to melt; a small amount of X-UHMWPE is added to the UHMWPE, so that the comprehensive performance of the composite material can be greatly improved, and the wear resistance is greatly improved and the ductility is maintained. such as the addition of 25 wt.% of the 150 kGy radiation cross-linked x-uhmwpe to the composite prepared in conventional uhmwpe, the wear resistance was increased by 130% and the tensile strength of 90% and the ductility of 70% were maintained with respect to the original uhmwpe. (5) The mechanical behavior of UHMWPE/ MWCNTs composite material was studied by X-ray irradiation and blending, and the MWCNTs were added to UHMWPE to prepare the composite material. The structure of MWCNTs and the change of the mechanical properties of the composite were studied in detail. The results show that the surface chemical structure of MWCNTs is changed by X-ray irradiation, the defect is increased, but the morphology is small, and the addition of small amount of radiation-modified MWCNTs can effectively improve the mechanical properties of the composite material, such as the addition of 2 wt% of the MWCNTs modified by the X-ray radiation can improve the yield strength of 20%; but it is difficult to effectively improve the thermal conductivity of the composite material by introducing a small amount of mwcnts.
【學(xué)位授予單位】：中國科學(xué)院研究生院(上海應(yīng)用物理研究所)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O632.12

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