3D打印PLA/PCL复合材料的力学性能

以聚己内酯(PCL)和聚乳酸(PLA)为实验原料,分别配比PCL质量分数在10%,20%和30%的PLA/PCL混合料,再经双螺杆挤出机挤出造粒后得到PLA/PCL复合材料。分别以纯PLA和3种不同配比的PLA/PCL复合材料为实验原料,使用粒料3D打印机制备拉伸、弯曲和冲击试件,并进行力学性能测试。结果表明,纯PLA试件的拉伸强度最大,为50.64 MPa,随着PCL含量的增加,试件的拉伸强度逐渐下降;试件的断裂伸长率随着PCL的含量的增加先增高后降低,当PCL质量分数为20%时,断裂伸长率达到最大值为25%;试件的弯曲强度随PCL含量的增加逐渐下降;试件的冲击强度随PCL含量的增加逐渐增大,当PCL质量分数为30%时,试件的冲击强度达到最大值,为15.80 kJ/m~2。     

不同分子量PCL增韧PLA的结构与性能

采用两种不同分子量的聚(ε-己内酯)(PCL)(粘均分子量60 000和3 000)与聚乳酸(PLA)在175℃下共混10 min制备PLA/PCL共混物。通过动态流变、扫描电子显微镜(SEM)和力学性能等研究了PLA/PCL共混物的结构和性能。动态流变显示,在PCL低含量(质量分数小于15%)时,PCL与PLA是相容的,质量分数为15%时PCL与PLA表现出明显的相分离行为。SEM显示,随着PCL含量的增加,PCL相的尺寸变大;低分子量PCL(L-PCL)的相尺寸明显大于高分子量PCL(H-PCL),而且相形态不是规则的球状。随着PCL含量的增加,共混物的拉伸强度下降,而断裂伸长率增加。当H-PCL质量分数为8.3%时,PLA/H-PCL共混物的断裂伸长率为137.32%。当H-PCL质量分数为15%时,其断裂伸长率高达232.76%。在添加相同含量PCL时,PLA/H-PCL共混物的拉伸强度高于PLA/L-PCL;而PCL质量分数8%时,共混物的断裂伸长率相差不多,当PCL质量分数大于8%时,PLA/H-PCL共混物的断裂伸长率明显比PLA/L-PCL共混物的高。     

PLA/PCL共混物的制备及其在医用材料中的应用

采用熔融共混法制备了聚乳酸(PLA)/聚己内酯(PCL)共混物,探讨了PCL含量对共混物加工性能和力学性能的影响。结果表明,随着PCL含量的增加,PLA与PCL在共混过程中的熔融转矩和平衡转矩总体呈下降趋势;拉伸强度逐渐降低,断裂伸长率先增加后减小,在PCL质量分数为30%时达到最大;冲击强度逐渐增大,当PCL质量分数超过30%时,增加幅度变缓。在此基础上利用超声波熔接技术将PLA/PCL共混物制成柔性肌腱吻合器,并以PCL质量分数为30%的共混物为例,研究了压力和辊压速度对肌腱吻合器外观质量的影响,发现在压力2.0 MPa、辊压速度5 mm/s的条件下可制备出外形良好、孔洞完好的肌腱吻合器。最后研究了在此工艺条件下由不同PCL含量的共混物制备的肌腱吻合器在体外模拟手术缝合过程中的性能,发现当PCL质量分数为30%时,肌腱吻合器显示出柔韧性好和不易拉豁等优点,在肌腱修复外科手术领域具有良好的应用前景。     

PLA/PBAT/OMMT生物基材料的制备及快速成型

对生物可降解材料聚乳酸(PLA)与聚己二酸对苯二甲酸丁二酯(PBAT)及有机蒙脱土(OMMT)材料进行共混,采用挤出成型制备PLA/PBAT/OMMT线材,再采用快速成型制备标准试样,通过对样件的力学性能、结晶行为、断面形貌和表观质量的测试和分析得出:纯PLA的拉伸强度和断裂伸长率分别为7.42MPa和1.8%,表现出硬而脆的特点;PLA/PBAT共混后,随着PBAT含量的增加,共混材料的断裂伸长率以及冲击强度不断提高,当PBAT含量为60%时,共混物的断裂伸长率达到405%,材料的冲击强度为31.11kJ/m2,约为纯PLA的11倍;而共混材料的拉伸强度表现出先增后减的趋势,当PBAT含量约为30%时,拉伸强度最佳,为37.08MPa;加入2%含量的OMMT后,共混材料的综合力学性能较之前又有不同程度的提高,其中拉伸强度以及冲击强度提升的较为明显;通过差示扫描量热和扫描电镜分析,PLA/PBAT共混体系为不相容体系,两相界面存在大量的孔洞,且结晶性能差,为半结晶聚合物,OMMT的加入使PLA/PBAT的两相界面变得模糊,极大地改善他们的相容性,而且还提高了共混物的结晶度;通过观察打印制件的表观质量,当PBAT的含量在30%左右,综合快速成型性能最佳。     

有机硅改性聚氨酯增韧聚乳酸的研究

针对聚乳酸(PLA)韧性差的特点,采用有机硅改性热塑性聚氨酯(TPSiU)对PLA通过熔融共混进行增韧改性,考察了TPSiU含量对PLA/TPSiU共混物微观结构、热性能及力学性能等的影响。研究结果表明,TPSiU的加入,使PLA由脆性材料转变为韧性材料,共混物的拉伸强度、弹性模量,冲击强度均随TPSiU含量的增加呈先增大后减小的趋势,当TPSiU的质量分数为20%时,PLA/TPSiU共混物的断裂伸长率提高约8倍。PLA/TPSiU共混物中两相呈海-岛结构,相容性欠佳,而且随着TPSiU含量的增加,"岛"相尺寸逐渐增大。另外,TPSiU的加入对PLA的热性能稍有影响,当TPSiU质量分数为10%时,共混体系的耐热性与纯PLA相当。     

聚己内酯/聚乳酸/竹纤维复合材料制备及性能

以聚己内酯（PCL）和聚乳酸（PLA）共混物为基材,竹纤维（BF）作为增强材料,硅烷偶联剂为改性剂,通过模压成型制备了PCL/PLA/BF复合材料。研究了PCL和PLA质量比、BF质量分数、硅烷偶联剂用量以及模压温度对复合材料性能影响。结果表明,适宜的PCL/PLA质量比为1∶1,BF质量分数为40 %时BF/PCL/PLA复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值11.26 kJ/m2,12.68 MPa和5.2 %;硅烷偶联剂用量为1 %时复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值15.11 kJ/m2、13.15 MPa和5.8 %;模压温度为150 ℃时,复合材料的冲击强度、拉伸强度和断裂伸长率分别达到最大值14.51 kJ/m2、13.75 MPa和5.8 %。     

PLA/PHBV共混改性研究

采用熔融共混法制备了聚乳酸/聚(3-羟基丁酸-co-3-羟基戊酸酯)(PLA/PHBV)共混物,研究了PLA/PHBV质量比以及滑石粉(Talc)含量对PLA/PHBV共混物性能的影响。结果表明,随着PHBV含量的增加,PLA/PHBV的结晶度先降低后升高,断裂伸长率提高了21.81%,冲击强度提高了35.9%,拉伸强度下降;随着Talc含量的增加,PLA/PHBV/Talc的结晶度增大,冲击强度提高了12.4%,但是断裂伸长率和拉伸强度有所下降;在不显著降低拉伸强度和弯曲强度的前提下,PHBV的含量为20%(质量分数,下同)且Talc含量为1.5%时,复合材料的力学性能最优。     

丙烯酸酯接枝改性天然橡胶增韧聚乳酸

通过在天然橡胶(NR)分子链上接枝甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA),制备了三种丙烯酸酯接枝改性NR:NR-g-PMMA,NR-g-PBA和NR-g-(PMMA,PBA)。采用核磁共振氢谱对三种接枝物进行了化学结构鉴定。将接枝改性后的NR和未改性的NR与PLA采用哈克密炼机熔融共混,分别制备了PLA/NR,PLA/NR-gPMMA,PLA/NR-g-PBA和PLA/NR-g-(PMMA,PBA)共混物,研究了接枝改性NR和未改性NR含量对共混物力学性能和热性能的影响。各共混物的拉伸弹性模量和拉伸强度均随接枝改性NR和未改性NR含量的增加而降低,断裂伸长率和缺口冲击强度随接枝改性NR和未改性NR含量的增加而提高。其中,PLA/NR-g-PBA共混物的断裂伸长率和缺口冲击强度比其它共混物提高的幅度大,当NR-g-PBA的质量分数为5%时,PLA/NR-g-PBA共混物的断裂伸长率达到78%,缺口冲击强度为5.2 k J/m2,而纯PLA的断裂伸长率仅为7.7%,缺口冲击强度为2.5 k J/m2,说明NR接枝分子柔顺性较高的BA更有利于促进其与PLA共混物的韧性提高。热分析结果表明,PLA/NR-gPBA共混物的热稳定性相比于纯PLA也有所提高。     

PCL增韧PLA共混材料的制备与性能研究

在聚乳酸(PLA)基体中加入聚己内酯(PCL)、柠檬酸三丁酯(TBC),通过熔融共混制备了PLA/PCL共混材料,并对其相容性、力学性能、热性能等进行了研究。结果表明:PLA/PCL为不相容体系,TBC作为相容剂对体系的韧性和强度影响较大;在TBC的作用下,共混材料两相之间发生了酯交换反应,生成界面相容剂,降低了PCL分散相的尺寸,改善了两相之间的相容性,提高了共混材料的韧性。当PLA与PCL的质量比为80/20、TBC的质量分数占共混材料总质量的8%时,共混材料的断裂伸长率可达125%,冲击强度值可达9.83kJ/m2。同时,共混材料的冷结晶峰消失,结晶趋于完善。     

竹纤维质量分数对PCL/PLA/竹纤维复合材料性能的影响

将竹纤维(BF)与聚己内酯(PCL)、聚乳酸(PLA)熔融共混,通过模压工艺制备了PCL/PLA/BF增强复合材料。研究了BF质量分数对该复合材料力学性能、热稳定性以及熔融结晶行为的影响。结果表明:随着BF质量分数的增加,PCL/PLA/BF复合材料的冲击强度、拉伸强度和断裂伸长率均先增大后减小,并均在BF质量分数为40%时达到最大值,分别为11.26 k J/m2、12.68 MPa和5.2%;BF质量分数对PCL/PLA/BF复合材料的热稳定性无明显影响;BF的加入使得复合材料中PCL、PLA共混物的玻璃化转变温度降低,但不同BF质量分数的复合材料玻璃化转变温度变化不大;BF的加入使得复合材料结晶温度小幅提升,但结晶峰强度随着BF质量分数的增加而逐渐减弱。     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Novel polyurethane coating technology through glycidyl carbamate chemistry

Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins. Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol. The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate functional group is more reactive than a glycidyl ether group. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago, IL.     

Highly moisture-proof polysilsesquioxane coating prepared via facile sol-gel process

A highly moisture-proof polysilsesquioxane coating was obtained from a new bis-silylated precursor, which was synthesized from 3-aminopropyltriethoxysilane (APTES) and m-xylylene diisocyanate (m-XDI) in tetrahydrofuran (THF) and verified by ¹H MAS NMR. For direct comparison purposes, an SiO₂ coating was also prepared by the Stöber method using tetraethoxysilane (TEOS) as the reactant. Interestingly, the coating obtained from the polysilsesquioxane sol exhibited a much higher moisture resistance capability than its counterpart, which was attributed to its more compact feature between nanoparticles as characterized by N₂ absorption experiment and transmission electron microscopy (TEM). Furthermore, its high transparency of about 92% showed potential for application in the protection of optical crystals.