Fabrication of polyetheretherketone(PEEK)-based 3D electronics with fine resolution by a hydrophobic treatment assisted hybrid additive manufacturing method

Additive manufacturing(AM)is a free-form technology that shows great potential in the integrated creation of three-dimensional(3D)electronics.However,the fabrication of 3D conformal circuits that fulfill the requirements of high service temperature,high conductivity and high resolution remains a challenge.In this paper,a hybrid AM method combining the fused deposition modeling(FDM)and hydrophobic treatment assisted laser activation metallization(LAM)was proposed for manufacturing the polyetheretherketone(PEEK)-based 3D electronics,by which the conformal copper patterns were deposited on the 3D-printed PEEK parts,and the adhesion between them reached the 5B high level.Moreover,the 3D components could support the thermal cycling test from-55℃ to 125℃ for more than 100 cycles.Particularly,the application of a hydrophobic coating on the FDM-printed PEEK before LAM can promote an ideal catalytic selectivity on its surface,not affected by the inevitable printing borders and pores in the FDM-printed parts,then making the resolution of the electroless plated copper lines improved significantly.In consequence,Cu lines with width and spacing of only60μm and 100μm were obtained on both as-printed and after-polished PEEK substrates.Finally,the potential of this technique to fabricate 3D conformal electronics was demonstrated.

CF增强PEEK复合材料原位成型与容器性能研究

采用激光原位铺放方法,制备了CF/PEEK复合材料层合板和压力容器,并通过内压爆破试验,对CF/PEEK压力容器的内压承载性能进行了表征。结果表明,研制的CF/PEEK压力容器有效爆破压强为18.33MPa,容器特性系数为40.3km,具有较为优异的内压性能。

Influence of CaCO_3 Whisker Content on Mechanical and Tribological Properties of Polyetheretherketone Composites

The mechanical and tribological properties of polyetheretherketone （PEEK） composites filled with CaCO3 whisker in various content of 0～45% （wt pct） were investigated. The composite specimens were prepared by compression molding. Tribological testing of composites in dry wear mode against carbon steel ring was carried out on a MM200 block-on-ring apparatus. Data on neat PEEK were also included for comparison. It was observed that inclusion of CaCO3 whisker affected the most mechanical properties and the friction and wear in a beneficial way. With an increase in CaCO3 whisker content, friction coefficient continuously decreased but the trends in wear performance varied. The specific wear rate showed minima as 1.28×10^-6 mm^3/Nm for 25% CaCO3 whisker inclusion followed by a slow increase for further CaCO3 whisker addition. In terms of friction applications, when the tribological and mechanical properties are combined, the optimal content of CaCO3 whisker in the filled PEEK should be recommended as 15% to 20%. Fairly good correlations are observed in friction coefficient vs bending modulus and wear rate vs bending strength, confirming that the bending properties prove to be the most important tribology controlling parameters in the present work.

注塑发泡工艺对PEEK制品性能影响

聚醚醚酮(PEEK)作为最具代表性的特种工程塑料,由于其具有较好的力学性能已被广泛应用于航天和军事领域。采用超临界流体注塑发泡的方式制备了发泡聚醚醚酮,发泡制品的质量降低了21%(比强度为59.8),最低介电常数为2.47。泡孔结构的介入降低了制品的力学性能,但是,较好的减重效果使发泡制品仍然具有较好的比强度。探究了泡孔结构对发泡PEEK制品的介电性能的影响规律,结果表明,更宽的发泡层使样品中的气体含量更高,可以有效降低制品的介电常数。由于分子链的极化作用,PEEK试样在X波段存在明显的介电常数波动现象。结晶可以抑制分子链的极化,因此,较高的结晶度可以降低制品的介电常数。研究表明,定向调控PEEK发泡制品的介电性能提供了指导方向。

PEEK口腔生物材料的应用现状及前景

介绍了金属、陶瓷等传统口腔生物材料的优势与不足,聚醚醚酮(PEEK)在口腔医学领域应用的突出优势(卓越的理化性能、良好的生物兼容性及美观性)。综述了PEEK在口腔正畸(正畸弓丝、早期矫治器械和舌侧固定保持器)、口腔修复(冠修复体、桩核、固定局部义齿、可摘局部义齿及颌面赝复体)、口腔种植(口腔种植体、愈合基台和骨支架)、口腔颌面外科(颌骨和颞下颌关节重建)及牙周病学(牙周夹板和牙合垫)等多个领域的应用现状、存在的不足和面临的挑战。重点讨论了通过PEEK改性以提升其在临床应用中的性能和适用性的多种方法。最后对PEEK在口腔医学领域的未来应用前景和发展方向进行了展望。

Resistance welding of carbon fibre reinforced polyetheretherketone composites using metal mesh and PEI film

Weldability of polyetheretherketone(PEEK) with polyetherimide(PEI) is tested. And carbon fiber reinforced PEEK laminates are resistance welded using stainless steel mesh heating element. The effects of the welding time and welding pressure on the lap shear strength of joints are investigated. Results show that PEEK can heal with PEI well in welding condition and the lap shear strength of PEEK/CF(carbon fibre) joint increases linearly with welding time, but reaches a maximum value when welding pressure ranging from 0.3 MPa to 0.5 MPa with constant welding time. The fracture characteristics of surface are analyzed by SEM techniques, and four types of fracture modes of lap shear joints are suggested.

Biocompatibility of polyetheretherketone for the treatment of orbital bone defects

AIM: To investigate the biocompatibility and therapeutic effects of polyetheretherketone(PEEK) on recovery of a rabbit orbital defect.METHODS: Totally 16 New Zealand rabbits were used to establish an orbital bone defect model and then randomly divided into two groups. PEEK was implanted in the experimental group. The control group was blank, and no substance was implanted. The model rabbits were sacrificed at 4 and 8 wk, and examined by general observations, histology, electron microscopy, Western blotting, and realtime polymerase chain reaction.RESULTS: No infection or rejection occurred after PEEK implantation, and biocompatibility was good. The relative expression of vascular endothelial growth factor(VEGF) protein in the experimental group was significantly higher than that in the control group postoperatively(P<0.05). Bone defect repair in the experimental group was significantly better than that in the control group in the same period and some osteogenesis was observed.CONCLUSION: PEEK has good biocompatibility and efficacy for the treatment of orbital bone defects in a rabbit model.

喷油润滑下PEEK齿轮的疲劳失效临界转变关系

聚醚醚酮(polyetheretherketone,PEEK)齿轮是高性能聚合物齿轮,广泛应用于汽车、无人机、机器人等领域。然而PEEK齿轮失效的形式和机理复杂,导致其在动力传动场合应用缺乏合理的设计依据。针对PEEK齿轮失效机理不明和基础数据缺失的问题,开展了喷油润滑下PEEK斜齿轮疲劳性能试验,计算了PEEK齿轮接触和弯曲应力,并通过扫描电镜等设备进行了失效表征。发现喷油润滑下PEEK齿轮失效形式主要为齿面点蚀和齿根疲劳断裂;讨论了喷油润滑下PEEK齿轮齿面点蚀与齿根疲劳断裂的失效机理,发现了PEEK齿轮接触疲劳失效与弯曲疲劳失效之间的临界转变关系,并提出了PEEK齿轮失效形式的评估方法。当PEEK齿轮接触应力与弯曲应力之比低于1.02时,PEEK齿轮主要发生齿根疲劳断裂;接触应力与弯曲应力之比高于1.10时,PEEK齿轮主要发生齿面点蚀破坏;接触应力与弯曲应力之比在1.02~1.10之间时,存在齿面接触疲劳与齿根弯曲疲劳的临界失效转变点。

Biomechanical Effects of Implant Materials on Posterior Lumbar Interbody Fusion: Comparison of Polyetheretherketone and Titanium Spacers Using Finite Element Analysis and Considering Bone Density

Few biomechanical data exist regarding whether the polyetheretherketone (PEEK) spacer or titanium spacer is better for posterior lumbar interbody fusion (PLIF). This study evaluated the biomechanical influence that these types of spacers with different levels of hardness exert on the vertebra by using finite element analysis including bone strength distribution. To evaluate the risk of spacer subsidence for PLIF, we built a finite element model of the lumbar spine using computed tomography data of osteoporosis patients. Then, we simulated PLIF in L3/4 and built models with the hardness of the interbody spacer set as PEEK and titanium. Bones around the spacer were subjected to different load conditions. Then, fracture elements and some stress states of the two modalities were compared. In both models of PLIF simulation, fracture elements and stress were concentrated in the bones around the spacer. Fracture elements and stress values of the model simulating the PEEK spacer were significantly smaller compared to those of the titanium simulation model. For PLIF of osteoporotic vertebrae, this suggested that the PEEK spacer is in a mechanical environment less susceptible to subsidence caused by microfractures of bone tissue and bone remodeling-related fusion aspects. Therefore, PEEK spacers are bio-mechanically more useful.

短切CF/PEEK复合材料的制备及抗紫外老化性能

CF/PEEK复合材料因轻质高强、耐腐蚀抗老化等特点,在各领域中被广泛应用,而其在成型过程中不可避免地会产生边料、废料,因此针对CF/PEEK回收再利用的研究很有意义。由于PEEK熔点高、溶体粘度大等特点,此类材料回收再利用困难,本工作通过添加一定量的PEEK树脂粉末的方法,改善短切预浸料的热压工艺性,通过紫外线加速老化实验,研究紫外老化对复合材料微观形貌、力学性能等的影响,并结合主成分分析法综合评价短切CF/PEEK复合材料的抗紫外老化性能,为热塑性预浸料和热塑性复合材料制品的回收再利用提供参考。研究结果表明:添加了树脂粉末的复合材料表面质量和力学性能得到明显的提高。试样表面的树脂基体在紫外老化作用下会出现粉化开裂并逐渐脱落的现象,在表面形成孔洞、裂纹等缺陷,紫外老化时间越长,复合材料表面受损越严重,力学性能下降越明显。通过主成分分析法得到,树脂添加量对短切CF/PEEK复合材料的抗紫外老化性能影响不大。

SULFONATION OF A NEW POLYETHERETHERKETONE PREPARED FROM PHENOLPHTHALEIN

A novel polyetheretherketone (PEK-C) prepared from phenolphthalein has been synthesized. In order to improve some of its properties for application in high performance membrane, the PEK-C has been sulfonated with concentrated sulfuric acid. Degree of sulfonation can be regulated by controlling the temmperature and time of sulfonation. The characterization of the sulfonated PEK-C in sodium salt form has been made by IR, ~1H NMR and ^(13)C NMR etc. It is shown that the sulfonation appears to take place exclusively in the ortho position to phenolic ether of phenolphthalein unit. The result is in agreement with theoretical deduction. Some properties of the sulfonated PEK-C, such as solubility, transition temperature, thermal degradation and hydrophilicity have also been discussed.

PEEK填充PTFE摩擦学性能的分子动力学模拟分析

采用分子动力学的模拟研究方法,建立不同质量比的聚醚醚酮(PEEK)填充聚四氟乙烯(PTFE)复合材料的无定型模型(PEEK质量分数分别为5%、10%、15%、20%),对模型进行几何优化和动力学优化,并构建PEEK/PTFE复合材料与Fe摩擦副对摩模型。模拟分析结果显示:质量分数10%PEEK填充的PEEK/PTFE复合材料的耐磨特性最佳,其磨损率与PTFE材料相比降低了26.44%,且减摩特性保持良好。通过分析摩擦界面处的结合能可以得出,在纯PTFE基材中加入PEEK可有效降低摩擦界面处的结合能,降低PTFE与对偶面的相互作用,从而降低磨损。通过分析摩擦界面处的原子含量、径向分布函数以及自由体积分数可以得出,质量分数为10%的PEEK/PTFE复合材料的PEEK和PTFE分子链分布更加均匀;然而PEEK质量分数过高时,晶胞内易出现不均匀变形和应力集中现象,使得PTFE分子在摩擦过程中更易出现脱落现象,耐磨性降低。研究结果从原子尺度揭示了PEEK对PTFE材料摩擦学性能的作用机制,从微观视域揭示了PEEK填充PTFE的增强机制,为研发新型PTFE基复合材料提供理论参考。

AN INVESTIGATION ON THE LOW TEMPERATURE RELAXATION OF POLYETHERETHERKETONE

The temperature spectra of internal friction of polyetheretherketone (PEEK) are investigated from 130K to 250K with a multi-function torsion pendulum in the frequency range of 0.1 Hz to 5 Hz. A relaxation process, γ relaxation, appears in the temperature range of the measurement. Its relaxation time distribution in terms of a Gaussian distribution, and the relation between molecular motion mechanism and the distribution characteristic are discussed. The element process of γ relaxation is found to be a disordering one.

层间熨平法增强熔丝制造CF/PEEK复合材料的力学性能

为减小熔丝制造(FFF)3D打印碳纤维增强聚醚醚酮(CF-PEEK)复合材料的孔隙率,提高其力学性能,提出一种层间熨平方法,即打印完一层后,喷嘴不挤出材料,并再次在这一层表面压过“熨平”。采用FFF工艺制备了CF/PEEK复合材料试样,通过单因素试验研究了扫描间距和层间熨平角度对CF/PEEK复合材料力学性能的影响。使用微米X射线三维成像系统对试样的内部孔隙缺陷进行表征。结果表明,当扫描间距为0.3 mm,纤维质量分数为10%时,无熨平CF/PEEK试样的孔隙率为1.91%,拉伸强度为78.5 MPa,弯曲强度为111.2 MPa。采用层间熨平法可以显著降低CF/PEEK复合材料试样的孔隙率,提高其力学性能。0°和90°熨平后,扫描间距为0.5 mm的CF/PEEK试样的孔隙率分别降低了74.08%和72.48%,拉伸强度分别提高了49.89%和41.98%,弯曲强度分别提高了20.66%和15.99%。当纤维质量分数为10%时,扫描间距0.3 mm的CF/PEEK试样的力学性能最佳,0°熨平的拉伸强度为90.9 MPa,90°熨平的弯曲强度为126.1 MPa。研究表明,层间熨平是一种降低孔隙率和提高力学性能的简单而有效的方式。

纳米ZrO_(2)增强PEEK/PTFE复合材料摩擦行为分子动力学模拟

为了从微观结构探究和揭示纳米二氧化锆(ZrO_(2))对聚醚醚酮(PEEK)/聚四氟乙烯(PTFE)复合材料摩擦行为的影响,在10%PEEK/PTFE复合材料中,分别添加质量分数4%、6%、8%、10%的纳米ZrO_(2),制备4种纳米ZrO_(2)填充PEEK/PTFE复合材料,并基于分子动力学(MD)方法构建4种复合材料与铁对摩的摩擦模型。结果表明:适量纳米ZrO_(2)可增强PEEK/PTFE复合材料分子链抵抗剪切变形的能力,在聚合物分子链之间形成较强的范德华力,改善了PEEK/PTFE复合材料摩擦性能;纳米ZrO_(2)在摩擦过程中能有效抑制层间滑移现象,在复合材料中起到吸附聚合物分子链的作用,增强了原子间相互作用,阻碍摩擦过程分子链内部滑移;其中质量分数6%纳米ZrO_(2)填充的复合材料摩擦性能最佳。

不同摩擦配副对PEEK及CF/PEEK复合材料摩擦学性能的影响

为了选择与PEEK及其CF改性复合材料更合适的配副材料以适应苛刻的干摩擦工况,本工作选用PEEK、CF/PEEK复合材料为研究对象,利用UMT-2型多功能摩擦磨损试验机在不同速度、载荷下对PEEK、CF/PEEK复合材料与Al 2O 3球、GCr15球、Si_(3)N_(4)球三种不同对磨球所组成的摩擦副进行干摩擦试验。结果表明:CF填充改性PEEK基复合材料,提高了复合材料的摩擦学性能。研究速度、载荷对其摩擦学性能的影响发现,三种对磨球所组成的摩擦副在固定载荷高速时或者固定速度重载时仍保持良好的摩擦磨损性能。三种对磨球中,GCr15轴承钢球与PEEK、CF/PEEK组成的摩擦副摩擦系数最大,磨损率最高;Si_(3)N_(4)陶瓷球的摩擦副摩擦系数最小,磨损率最低。当GCr15-CF/PEEK摩擦副在50 N、400 r/min高速时,摩擦系数为0.275,在90 N、300 r/min重载下,摩擦系数为0.254;当Si_(3)N_(4)-CF/PEEK摩擦副在50 N、400 r/min高速时,摩擦系数为0.265,在90 N、300 r/min重载下,摩擦系数为0.231。GCr15-CF/PEEK摩擦副盘试样在高速高载的苛刻工况下发生了严重的磨粒磨损和黏着磨损,而Si_(3)N_(4)-CF/PEEK摩擦副盘试样在高速高载的苛刻工况下主要是磨粒磨损和轻微的黏着磨损。

抗菌性碳点修饰PEEK干预MRSA感染环境植入物骨整合性能的体内研究

目的本研究拟评价抗菌性碳点修饰聚醚醚酮(polyether ether ketone,PEEK)在感染性骨缺损环境的骨整合性能。方法熔融法制备结合透析纯化获得胍基碳点(guanidine-based carbon dots,G-CDs),应用聚乙烯醇缩丁醛酯(polyvinyl butyral,PVB)通过浸泡-干燥法制备G-CDs修饰的PEEK植入物(PEEK/PVB-G-CDs)。将SD大鼠分为:PEEK植入未感染组(PEEK(-)组),PEEK/PVB-G-CDs植入未感染组(PEEK/PVB-G-CDs(-)组),PEEK植入感染组(PEEK(+)组),PEEK/PVB-G-CDs植入感染组(PEEK/PVB-G-CDs(+)组)。每组大鼠均于垂直股骨外侧髁处制备一个直径2 mm、深度5 mm的孔洞以模拟骨缺损。将30μL生理盐水注入PEEK(-)组和PEEK/PVB-G-CDs(-)组大鼠骨缺损的骨髓腔内形成未感染组。将30μL耐甲氧西林金黄色葡萄球菌(Methicillin-resistant Staphylococcus aureus,MRSA)菌悬液(1.5×10^(4) CFU/mL)注入PEEK(+)组和PEEK/PVB-G-CDs(+)组大鼠骨缺损的骨髓腔内。植入术后0、2和4周,应用动物专用X射线机照射各组大鼠植入部位。术后6周,Micro-CT评估植入部位的骨组织特征。骨髓细菌培养、苏木精-伊红染色(HE staining)、甲苯胺蓝染色(Toluidine blue staining)、戈德纳三色染色(Goldner trichrome staining)及免疫组化染色分析各组大鼠的骨植入部位。结果(1)X射线、Micro-CT、骨髓细菌培养和组织病理学分析等结果确定证实了PEEK(-)组和PEEK/PVB-G-CDs(-)组未出现感染与骨缺损整合;PEEK/PVB-G-CDs(+)组发挥抗菌性有效控制MRSA,菌株形成的骨髓炎实现骨整合,而PEEK(+)组因持续的感染无法骨整合;(2)免疫组化染色评价明确PEEK(+)组显示出比其他3组更低的白细胞介素(interleukin,IL)-4和IL-10等抗炎因子以及更强的IL-6和肿瘤坏死因子(tumor necrosis factor,TNF)-α等促炎因子表达,表明G-CDs修饰的PEEK可抑制MRSA感染,调节局部微环境的炎症水平,促进骨缺损部位的骨整合。结论抗菌性碳点修饰PEEK具备优异的骨整合性能,为今后的临床治疗提供了一种候选策略。

3D打印工艺参数对聚醚醚酮(PEEK)介电性能的影响

为研究3D打印工艺对聚醚醚酮(PEEK)介电性能的影响,基于熔融沉积成型技术,选择多种工艺参数进行单因素实验,针对喷头温度、基板温度、打印速度、层厚、腔室温度等工艺进行研究。实验结果表明:在喷头温度400℃、基板温度140℃、打印速度30 mm/s、层厚0.1 mm、腔室温度120℃时PEEK样件介电常数最低;1~100 MHz频段内频率对介电常数无影响;1~40 MHz频率内,各工艺参数测试得到的PEEK介电损耗角正切均大幅波动;在40~100 MHz频率内,PEEK介电损耗角正切均呈现波动上升的趋势。该研究结果将为天线PEEK介质层的结构设计和制造提供依据。

3D打印C-PEEK的仿生结构设计和力学行为分析

为了分析3D打印碳纤维增强聚醚醚酮(C-PEEK)复合材料的力学行为,探索最优工艺参数进行仿生结构设计,研究了碳纤维含量、打印喷头温度、平台温度、切片层厚度、打印速度、填充度、填充直线角度、填充形状、热处理温度及保温时间等多个工艺参数下,3D打印C-PEEK的力学性能演化规律。结果表明:含10 wt.%碳纤维的C-PEEK拉伸性能最好,并且最佳的3D打印参数为:打印喷头温度440℃、平台温度130℃、切片厚度0.2mm、填充度100%、90°直线填充、打印速度40mm/s、保温腔90℃。此外,根据最佳3D打印参数设计兼具蜂窝多孔和Bouligand旋转夹层的仿生结构,开展抗压强度测试并进行压溃行为分析,发现当层间旋角为30°时对应的蜂窝-Bouligand仿生结构的抗压强度可达24.1 MPa,且具有优异的非灾难性断裂特征。