Welding of Thermoplastic Matrix Composites

Total Page:16

File Type:pdf, Size:1020Kb

Welding of Thermoplastic Matrix Composites Welding of Thermoplastic Matrix Composites: Prediction of Macromolecules Diffusion at the Interface Gilles Régnier, Célia Nicodeau, Jacques Verdu, Francisco Chinesta, Virginie Triquenaux, Jacques Cinquin To cite this version: Gilles Régnier, Célia Nicodeau, Jacques Verdu, Francisco Chinesta, Virginie Triquenaux, et al.. Weld- ing of Thermoplastic Matrix Composites: Prediction of Macromolecules Diffusion at the Interface. 8th ESAFORM Conference on Material Forming, 2005, Cluj-Napoca, Romania. hal-00020871 HAL Id: hal-00020871 https://hal.archives-ouvertes.fr/hal-00020871 Submitted on 12 Mar 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Welding of thermoplastic matrix composites: prediction of macromolecules’ diffusion at the interface G. Régnier1, C. Nicodeau1, J. Verdu1, F. Chinesta2, V.Triquenaux3, J.Cinquin3 1Laboratoire de Transformation et de Vieillissement des Polymères ENSAM 151, Bd de l’Hôpital 75013 Paris e-mail: [email protected]; 2Laboratoire de Mécanique des Systèmes et des Procédés, UMR CNRS 8106 ENSAM 151, Bd de l’Hôpital 75013 Paris e-mail: [email protected]; 3EADS CCR 5, quai Marcel Dassault BP76 92152 Suresnes Cedex e-mail: [email protected]; ABSTRACT: The automated tow placement process allows to fabricate thermoplastic composite parts by welding of pre-impregnated plies. In order to describe the phenomenon of welding for a Carbon/PEEK composite by interdiffusion of polymer chains across the interface between two plies, a simulation of the process, which predicts the material thermal history, is done. The reptation time linked to chain diffusion is estimated by rheological experiments and extrapolated at high temperatures. Although the material only remains a very short time above its melting temperature, it is showed that, under appropriate process conditions, this welding process is promising. Key words: in situ consolidation, thermoplastic composite tape, relaxation time, chains diffusion whether or not the welding is possible under 1 INTRODUCTION industrial constraints. The optimisation of the process will eventually follow. Firstly, it is The automated tow placement process, developed in necessary to describe and model the physical the aircraft industry by EADS, Dassault Aviation phenomena taking place at the interplies. The APC-2 and Eurocopter, is an emerging technique for (UD Carbon/PEEK pre-impregnated) composite will manufacturing continuous fiber-reinforced be used for this study. thermoplastic parts. The consolidation is performed by the machine head, realising a welding phenomenon between the two plies as shown in 2 MACROMOLECULAR CHAINS DIFFUSION figure 1. Two torches first heat the incoming tape THEORY and the already-laid down substrate at a temperature greater than the resin melting temperature. Then a Once the intimate contact between plies is compaction roller applies a normal force in order to established, the interdiffusion of macromolecular improve the intimate contact between the plies. chains at the interface occurs as long as the matrix is Roller (P,T) melt, i.e before crystallisation quenches movements. This achieved the adhesion phenomenon. Velocity v The reptation theory introduced by De Gennes [1] Torches (T) and Doi & Edwards [2] models the motion of v individual linear polymer chains in the bulk. In the model, a polymer chain of length L, is considered to Fig. 1. In situ consolidation process for thermoplastic tapes be confined in a tube, which represents the steric Process parameters such as lay-down velocity, effects of neighbourhood chains via entanglements torches and roller temperatures and compaction [3]. The chain can only move along the tube pressure will determine the interfacial bonding curvilinear length as shown in figure 2. The chain quality. The aim of this study is to determine moves within the tube in a Brownian motion 1 manner, and after a period of time t, the chain ends Viscoelastic phenomena are the consequence of escape from the original tube, forming the “minor chains intra- or intermolecular motions around their chains” of length l(t) [4]. During this process l(t) equilibrium configuration. The notion of “relaxation increases with time until it reaches L at the reptation time” describes the dependence of time -shear rate time tR. Beyond the reptation time, the entire or frequency- on viscoelastic properties. polymer chain is out of the tube, the interpenetration The longer the relaxation time is, the larger the and entanglement of all the polymer chain is fully spatial scale of possible motions [8]. If the frequency developed at the interface and the molecular is smaller than the transition frequency between the configuration is identical to that of the bulk material. rubbery plateau and the terminal zone, the minor observation period of time of macromolecular chains chain l(t) is greater than entanglements life time. Thus, the tube terminal zone -“long times” zone- describes the displacement along the entire polymer chain. For the chain description of the consolidation process, our aim is entanglement to evaluate this terminal relaxation time λ, referred Fig. 2. Reptation model as “long time”, which is the longest time for the De Gennes [5] represents chain motion by migration polymer chain. of certain “defects” along the chain. De Gennes 3 3.2 Dynamic tests showed that tR= M where M is the molecular weight of the linear chain. Doi and Edwards [6] showed the Experiments have been realised on pure PEEK same relation using a diffusion equation. However, it (G450; average molar mass in weight and in number is not possible in our case to determine a numerical Mw=106900g/mol and Mn=37000g/mol). reptation time from their theoretical expressions. Unfortunately, exact characteristics of the PEEK That is the reason why we will approach this used for APC-2 cannot be known; however, relaxation time thanks to rheological experiments. according to the supplier, this grade G450 represents In order to study the diffusion phenomenon the highest boundary in terms of molecular weight. associated to this process, it is necessary to evaluate The dynamic shear measurements were performed the temperature field of a composite part during its on a rheometer (ARES Rheometric Scientific), with processing. A 2D model has been developed [7]. It is parallel plates geometry. Several isothermal tests based on an explicit numerical scheme that takes were made under nitrogen atmosphere at into account the heat transfer via conduction and temperatures in the range of 310°C to 410°C (glass convection as well as source terms due to material transition temperature Tg=140°C and melting crystallisation and melting. This calculation gives temperature Tm=330°C). A periodic strain with a the dependence of the temperature field in a multi- fixed amplitude (2% in order to be in the linear layered composite part -particularly the temperature viscoelastic zone) is imposed to the sample. The at a chosen interface- on the process parameters. An frequency sweep is performed between 100 and 0.01 experimental study is then carried out in order to rad/s. validate the numerical computation results. In the current study, we will focus on 3.3 Relaxation time & models macromolecular chains diffusion and other phenomena such as polymer crystallisation or Several analyses are possible to determine “long” thermal degradation won’t be discussed. relaxation time relative to reptation phenomenon We will use interfacial time-temperature history from experimental results: given by the model and we will explain the method • From intersection of G’ and G’’(elastic and which leads to conclusions on whether the welding viscous component of complex modulus) tangents phenomenon is possible or not. when ω tends to 0 [9]. However, in our case, complementary creep tests would be necessary to get G’ values at smaller frequencies. 3 EXPERIMENTAL STUDY • From the viscosity values; we consider 3.1 Introduction transition between newtonien state –characteristic of the intermolecular friction and which is obtained 2 when every molecule is relaxed- and the The dynamic measurements were performed on the rheofluidifiant regime -for which the viscosity rheometer at temperatures in the range of 310°C to follow the power law model- [10]. Yasuda and 410°C. We note that, for these temperatures Carreau’s equation applied to shear rate gives the conditions, the “long times” fit the Arrhenius’ law, relation of the viscosity η [11]: as the newtonian viscosity. Hence, Figure 4 shows a (m-1)/a the extrapolation of long times at higher η = η0{1+ (λ ) } (1) temperatures typical of adhesion phenomenon on the with ηo(T) the newtonian viscosity, λ(T) the process. transition characteristic time between newtonien and pseudo-plastic regime, a a parameter relative to the 10 curvature of this transition and depending on the material polydispersity index and m the flow index. 1 0,001 0,0014 0,0018 The intersection point abscise of asymptotes defined 325°C at boundary frequencies gives hence the condition 0,1 600°C ω=1/λ and enables us to determine Carreau’s law 410°C relaxation time λ(T) as shown in figure 3. Here, for (s) time "long"relaxation example, the average “long” time at 360°C is 900 0,01 1/T (K-1) ms. ηo is given by the value of the plateau viscosity and Fig. 4. “Long time extrapolation” according to the Arrhenius’ fit the Arrhenius’ law. Parameters of Yasuda & law Carreau’s corresponding to our experimental values Our aim is to apply these results on time- are: a=0.7 and m=0.54.
Recommended publications
  • Microrheometry of Semiflexible Actin Networks Through Enforced Single-Filament Reptation: Frictional Coupling and Heterogeneities in Entangled Networks
    Microrheometry of semiflexible actin networks through enforced single-filament reptation: Frictional coupling and heterogeneities in entangled networks M. A. Dichtl† and E. Sackmann Lehrstuhl fu¨r Biophysik E22, Technische Universita¨t Mu¨ nchen, James-Franck-Strasse, D-85747 Garching, Germany Edited by Harden M. McConnell, Stanford University, Stanford, CA, and approved December 27, 2001 (received for review August 16, 2001) Magnetic tweezers are applied to study the enforced motion of filaments embedded in networks may be visualized and analyzed single actin filaments in entangled actin networks to gain insight by fluorescence microscopy (16) or by labeling with colloidal into friction-mediated entanglement in semiflexible macromolec- probes (17). In previous work, the latter possibility was used to ular networks. Magnetic beads are coupled to one chain end of test relate macroscopic viscoelastic impedance spectra to thermally filaments, which are pulled by 5 to 20 pN force pulses through driven single-filament motion. entangled solutions of nonlabeled actin, the test filaments thus The frequency-dependent viscoelastic impedance G*(␻) ϭ acting as linear force probes of the network. The transient filament GЈ(␻) ϩ iGЉ(␻) exhibits three distinct frequency regimes (18): at ␯ ϭ ␻͞ ␲ Ͼ ͞␶ ␶ Ͼ Ϫ2 ␶ motion is analyzed by microfluorescence, and the deflection- high frequencies, 2 1 e [ e 10 sec; note that e versus-time curves of the beads are evaluated in terms of a is the relaxation time of the bending mode of a chain segment of ⌳ mechanical equivalent circuit to determine viscoelastic parameters, length equal to the entanglement length e (6)], the shear elastic which are then interpreted in terms of viscoelastic moduli of the modulus GЈ(␻)Љ and the loss modulus GЉ(␻) increase with network.
    [Show full text]
  • Arxiv:1802.03702V1 [Cond-Mat.Soft] 11 Feb 2018 Relaxation Remain Controversial for Several Reasons
    Disentangling Entanglements in Biopolymer Solutions Philipp Lang and Erwin Frey∗ 1Arnold Sommerfeld Center for Theoretical Physics and Center for NanoScience, Department of Physics, Ludwig-Maximilians-Universität München, Theresienstrasse 37, 80333 München, Germany Reptation theory has been highly successful in explaining the unusual material properties of entangled polymer solutions. It reduces the complex many-body dynamics to a single-polymer description where each polymer is envisaged to be confined to a tube through which it moves in a snake-like fashion. For flexible polymers, reptation theory has been amply confirmed by both experiments and simulations. In contrast, for semiflexible polymers experimental and numerical tests are either limited to the onset of reptation, or were performed for tracer polymers in a fixed, static matrix. Here we report Brownian dynamics simulations of entangled solutions of semiflexible polymers, which show that curvilinear motion along a tube (reptation) is no longer the dominant mode of dynamics. Instead, we find that polymers disentangle due to correlated constraint release which leads to equilibration of internal bending modes before polymers diffuse the full tube length. The physical mechanism underlying terminal stress relaxation is rotational diffusion mediated by disentanglement rather than curvilinear motion along a tube. Dense solutions of polymers are viscoelastic: While agarose networks seem to support Odijk’s scaling result[3] 2 they respond like a fluid to low-frequency stresses, they τr ∼ `pL . However, these experimental results do not act like a cross-linked elastic network at high frequen- settle the actual controversy, as the polymer diffuses in a cies. These intriguing material properties are attributed fixed, static matrix and not in an entangled polymer solu- to the extended structure of polymers, which makes topo- tion.
    [Show full text]
  • Neutron Scattering from Polymers 3 CH07CH01-Higgins ARI 14 May 2016 9:6
    CH07-FrontMatter ARI 14 May 2016 8:27 Access provided by University of Cincinnati on 02/03/17. For personal use only. Annu. Rev. Chem. Biomol. Eng. 2016.7:1-28. Downloaded from www.annualreviews.org CH07CH01-Higgins ARI 14 May 2016 9:6 ANNUAL REVIEWS Further Click here to view this article's online features: • Download figures as PPT slides • Navigate linked references • Download citations Neutron Scattering from • Explore related articles • Search keywords Polymers: Five Decades of Developing Possibilities J.S. Higgins Department of Chemical Engineering, Imperial College London, London SW7 2AZ, United Kingdom Annu. Rev. Chem. Biomol. Eng. 2016. 7:1–28 Keywords The Annual Review of Chemical and Biomolecular neutron scattering, polymer molecular dynamics, polymer blends, spinodal Engineering is online at chembioeng.annualreviews.org decomposition, polymer interfaces Access provided by University of Cincinnati on 02/03/17. For personal use only. This article’s doi: Annu. Rev. Chem. Biomol. Eng. 2016.7:1-28. Downloaded from www.annualreviews.org 10.1146/annurev-chembioeng-080615-034429 Abstract Copyright c 2016 by Annual Reviews. The first three decades of my research career closely map the development All rights reserved of neutron scattering techniques for the study of molecular behavior. At the same time, the theoretical understanding of organization and motion of polymer molecules, especially in the bulk state, was developing rapidly and providing many predictions crying out for experimental verification. Neu- tron scattering is an ideal technique for providing the necessary evidence. This autobiographical essay describes the applications by my research group and other collaborators of increasingly sophisticated neutron scattering tech- niques to observe and understand molecular behavior in polymeric materials.
    [Show full text]
  • Experimental Tests of Polymer Reptation
    Copyright is owned by the Author of the thesis. Permission is given for a copy to be downloaded by an individual for the purpose of research and private study only. The thesis may not be reproduced elsewhere without the permission of the Author. EXPERIMENTAL TESTS OF POLYMER REPTATION A thesis presented in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Physics at Massey University Michal Komlosh 1999 ABSTRACT Pulsed Gradient Spin Echo Nuclear Magnetic Resonance (PGSE-NMR) and rheology measurements were used to test whether the dynamics of entangled polymer chains in semidilute solution follow the reptation theory. Nine molar masses from 1 to 20 million daltons at a fixed concentration of 4.96% w/v along with a range of concentrations from 4.96% to 23.58% w/v at fixed molar mass of 3 million daltons were studied using PGSE-NMR techniques. The response to mechanical deformation of fivedif ferent concentrations from 4.96% to 23.58% w/v at fixed molar mass of 3.9 million daltons was also studied. The distance and time scales accessed by PGSE-NMR were 20 to 1000 nm and 10 to 3000 ms respectively. As a result the mean square segmental motion over three reptation regimes was obtained and the reptation fm ger l print, ((r(t) -r(O))) - t1 4 , was observed. The resulting concentration and molecular weight scaling laws for the disengagement time, center of mass diffusion and the tube tube diameter, which were obtained in PGSE-NMR and rheology experiments, were found to be in good agreement with the reptation theory and its standard modifications, and a good quantitative fit to the mean square displacement was given by this theory.
    [Show full text]
  • Professor Sir Sam Edwards 1.2.1928 – 7.7.2015 FRS 1966, Kt 1975
    Professor Sir Sam Edwards 1.2.1928 – 7.7.2015 FRS 1966, Kt 1975 By Mark Warner, FRS Sam Edwards was one of the leading physicists of the second half of the 20th Century. He was Cavendish Professor in the University of Cambridge, a Vice President of the Royal Society, a member of the Academy des Sciences and of the US National Academy, and a senior figure in the University and his College. He played a major role in public life, most notably as chairman of the Science Research Council, responsible for research funding in the UK. He was chairman of the British Association, chief government scientist to the Department of Energy, and Chairman of the Defence Scientific Advisory Council. He was equally in demand to lead or to help set up bodies abroad, particularly for the Max Planck Institute for Polymers in Mainz, Germany. Remarkably, Sam made some of his most celebrated scientific discoveries, for instance the theory of spin glasses and the rheology of high polymer melts, while serving as the full-time head of the SRC. Conversely, his scientific insights informed his leadership in advising the Government. His later science was in highly applicable areas; he was an active advisor to Unilever, Dow, Lucas, and many other companies that rely on research. Wales, Cambridge and the USA ‘I was born in Swansea on 1st February 1928. I was an only child but there was a large extended working class family. Soon after my birth, my father who had found a permanent job reading electric meters, bought a house in the suburb of Manselton where I was brought up.
    [Show full text]
  • The Longitudinal Superdiffusive Motion of Block Copolymer in A
    polymers Article The Longitudinal Superdiffusive Motion of Block Copolymer in a Tight Nanopore Waldemar Nowicki Faculty of Chemistry, Adam Mickiewicz University in Pozna´n,ul. Uniwersytetu Pozna´nskiego8, 61-614 Pozna´n, Poland; [email protected] Received: 7 November 2020; Accepted: 3 December 2020; Published: 8 December 2020 Abstract: The structure and dynamic properties of polymer chains in a confined environment were studied by means of the Monte Carlo method. The studied chains were represented by coarse-grained models and embedded into a simple 3D cubic lattice. The chains stood for two-block linear copolymers of different energy of bead–bead interactions. Their behavior was studied in a nanotube formed by four impenetrable surfaces. The long-time unidirectional motion of the chain in the tight nanopore was found to be correlated with the orientation of both parts of the copolymer along the length of the nanopore. A possible mechanism of the anomalous diffusion was proposed on the basis of thermodynamics of the system, more precisely on the free energy barrier of the swapping of positions of both parts of the chain and the impulse of temporary forces induced by variation of the chain conformation. The mean bead and the mass center autocorrelation functions were examined. While the former function behaves classically, the latter indicates the period of time of superdiffusive motion similar to the ballistic motion with the autocorrelation function scaling with the exponent t5/3. A distribution of periods of time of chain diffusion between swapping events was found and discussed. The influence of the nanotube width and the chain length on the polymer diffusivity was studied.
    [Show full text]