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Slip at polymer-polymer interfaces: Rheological measurements on coextruded multilayers

机译:聚合物-聚合物界面的滑移:共挤多层的流变学测量

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Polypropylene (PP) and polystyrene (PS), with closely matched viscosity, were coextruded into 8, 32, and 64 alternating layers. The apparent steady shear viscosity of these multilayer samples was measured with an in-line slit rheometer and with a parallel-plate rheometer. In both cases the apparent viscosity decreased with the number of layers providing strong evidence for interfacial slip. The velocity difference across the interface (interfacial slip velocity) versus shear stress, ΔV_I(τ) was calculated from the apparent viscosity measurements. ΔV_I(τ) showed sigmoidal behavior: a region of very low slip (<10~(-3) μm) at low shear stress, a strongly increasing region at τ > 10~3 Pa followed by a linear region ΔV_I = τ/β_∞. These data could be fit with a modified Ellis model. The same function fit the different number of layers and both slit and parallel-plate data indicating ΔV_I(τ) is a material property of the PP/PS pair. Slip was also observed in PS/PMMA (polymethyl methacrylate) and PP/aPA (amorphous nylon) pairs. Addition of a premade P(S-b-EE) diblock copolymer to the PP/PS pair was able to suppress the interfacial slip but only after enough time for sufficient block copolymers to diffuse to the interfaces. The in situ formed graft copolymer of maleated PP with aPA at the interface of the PP/aPA pair directly suppressed the slip. Our results are in qualitative agreement with the theory of Furukawa (1989) and de Gennes (1992), which predicts fewer chain entanglements near the interface between two immiscible polymers, and thus a narrow region (~interfacial width) with lower viscosity. This lower viscosity is the cause of apparent interfacial slip. Goveas and Fredrickson (1998) extended these ideas to calculate the slip in a symmetric bilayer where both bulk and interface are Newtonian. Their results are in qualitative agreement with our observation but predict a stronger slip. Our results also indicate that the anomalously low viscosity reported by a number of researchers for immiscible polymer blends is due to interfacial slip. Blends of PP and PS show similar negative viscosity deviations to those reported but only at τ > 2000 Pa. No negative deviations were found for linear viscoelastic (low-stress) measurements.
机译:将粘度紧密匹配的聚丙烯(PP)和聚苯乙烯(PS)共挤出为8、32和64个交替层。用在线狭缝流变仪和平行板流变仪测量这些多层样品的表观稳态剪切粘度。在这两种情况下,表观粘度均随层数的增加而降低,为界面滑移提供了有力的证据。从表观粘度测量值计算出界面上的速度差(界面滑移速度)与切应力的关系,ΔV_I(τ)。 ΔV_I(τ)呈S型曲线:在低剪切应力下非常低的滑动区域(<10〜(-3)μm),在τ> 10〜3 Pa处有一个强烈增加的区域,随后是线性区域ΔV_I=τ/β_ ∞。这些数据可以与修改后的Ellis模型拟合。相同的函数适合于不同的层数,并且缝隙和平行板数据均指示ΔV_I(τ)是PP / PS对的材料属性。在PS / PMMA(聚甲基丙烯酸甲酯)和PP / aPA(无定形尼龙)对中也观察到滑移。在PP / PS对中添加预制的P(S-b-EE)二嵌段共聚物能够抑制界面滑移,但只有在足够的时间后,足够的嵌段共聚物才能扩散到界面上。在PP / aPA对的界面处马来酸化的PP与aPA的原位形成的接枝共聚物直接抑制了滑移。我们的结果与Furukawa(1989)和de Gennes(1992)的理论在质量上吻合,后者预测两种不混溶的聚合物之间的界面附近的链缠结较少,因此粘度较低的狭窄区域(〜界面宽度)。较低的粘度是明显的界面滑移的原因。 Goveas和Fredrickson(1998)扩展了这些思想,以计算对称双层中的滑移,其中双层和界面均为牛顿型。他们的结果与我们的观察在质量上吻合,但预示着滑动会更强。我们的结果还表明,许多研究人员报告了不混溶的聚合物共混物的异常低粘度是由于界面滑移引起的。 PP和PS的共混物显示出与已报道的负粘度相似的负粘度偏差,但仅在τ> 2000 Pa时才存在。线性粘弹性(低应力)测量未发现负偏差。

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