VAMAS ACTIVITY INITIATION FORM The form should be generated by the proposer and it should contain the sections

shown below and be completed according to the instructions given. 1. Proposed Activity Please tick all that apply New Technical Working Area (TWA) X New Project

#3

in

Existing TWA-33

2. Proposed Theme/Title

Mechanical Testing of Polymer Nanocomposites

3. Proposed Activity and Objectives The objective of this project is characterization of the mechanical properties of polymer nanocomposites (PNC) and effects of their nano-sized filler particles (natural and synthetic clays) on the time-dependent properties of the base polymer by determining their quasi-static, dynamic, fracture properties, and nanoindentation behavior. 4. Proposers Dr. Martin N. Bureau, Eng., Industrial Materials Institute, National Research Council Canada, martin.bureau@cnrc-nrc.gc.ca, 1-450-641-5179 Dr. Volker Trappe, Federal Institute for Materials Research and Testing, BAM, Germany, volker.trappe@bam.de, +49 30 8104 3386 Dr. Michael Griepentrog, Federal Institute for Materials Research and Testing, BAM, Germany, michael.griepentrog@bam.de, +49 30 8104-3555

5. Background and Pre-standardization Needs At least two ISO standards (and their ASTM counterparts) are targeted here. Both relate to Linear Elastic Fracture Mechanics (LEFM) approaches to determine fracture toughness (GIC and KIC, ISO 13586) and tension-tension (mode I) fatigue crack propagation (FCP, ISO 15850). Both these measurements are used to determine the resistance of a materials to fracture or to crack propagation in the presence of a sharp crack under mode I conditions (crack opening) such that a state of plane strain prevails at the crack tip and that the plastic zone size (i.e., non-linear viscoelastic) is small compared to the non-deformed specimen dimensions. These measurements may reflect the relation between stress that may lead to crack propagation and the defect size for an in-service material component under similar stress conditions. Other modes of crack

loading [shear (or mode II) and torsion (mode III)] may also be considered using this approach, although these have not been standardized. Since fracture toughness and FCP measurements depend on plasticity and viscoelasticity of the material, and since nano-reinforcements induce profound changes in the base polymer with regards to these two properties, simple and straightforward comparison of measurements made on PNC and base polymer is not straightforward. For a better understanding of the fracture mechanics of PNC the exact knowledge of the mechanical properties of these nanomaterials (on global or local scale) like hardness, Youngs modulus, yield strength and stress strain behavior (elasto-plastic, viscoelastic) is of great importance. The test methods on the global scale like tensile or bending test, dynamic mechanical analysis (DMA) and macro hardness are well established and standardized. However, in the clay-infiltrated polymer blends, the average dispersion rate can be measured by sampling various cross-sections, but this number often does not correlate with the global property measured by bend bar tests or tensile tests. Since material property often depends on the critical defect population, particle agglomeration in a polymer blend is difficult to measure systematically. By inserting a particle or structuring local morphology on the nanometer scale, the global properties are modified. One of the key issues in nanomaterials testing is how to measure the nanoscale features that caused the property change and link the nano-scale to the global properties. The measurements are to be used for PNC specification containing nano-fillers or organo-nano fillers by any industry using nano-fillers in polymers, e.g., for flame retardancy, increased stiffness and tensile strength, improved barrier properties, dimensional stability, recyclability, greater clarity, HDT, etc. These measurements might also be used for quality control of finished PNC parts. Communication and reporting to the ISO TC 61/SC 2 is planned (Fracture Mechanics). Tests with local resolution in the nano range, especially instrumented indentation test (IIT) (Nanoindentation, AFM) are also standardized ISO 14577 1-4 (ISO TC 164/SC 3 Hardness testing) Metallic materials Instrumented indentation test for hardness and materials parameter (Part 4: Measurements for coatings); ISO TR 29381 (ISO TC 164/SC 3 Hardness testing) Metallic materials Measurement of mechanical properties by instrumented indentation test Indentation tensile properties; ASTM E-2806 New Standard Practice for Instrumented Indentation Testing; BS DD CEN/TS 1071-7 (CEN TC 164/WG 5); Advanced technical ceramics - Methods of test for ceramic coatings - Determination of hardness and Young's modulus by instrumented indentation testing. But all this standardization was done only for homogeneous materials.

Supplemental information for the VAMAS SC In light of the comments made by the SC members regarding the motivation behind the choice of ISO standards and our expectation that these standards would necessitate changes or modifications, we would like to bring to the attention of the SC members two publications (refs. 1, 2), Bureau and co-workers showed that the behavior of PA6based PNCs was affected by its viscoelastic response, which varied depending on its conditioning state and mechanical history. Indeed, the commercial, in situ polymerized
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PA6-based PNCs presented a shift in fracture behavior from its non-modified PA6 counterpart when conditioned (ref. 1), changing from linear elastic with crazing as predominant mode of fracture for PA6-based PNCs to elasto-plastic with shear yielding for PA6. This led to unreliable conclusions concerning the effect of nano-clay reinforcements on the fracture toughness of PA6. Since in practice, the conditioned state is the state of reference for such materials, reliable benchmarking fracture toughness data must be available and therefore the standard test methods for fracture toughness might have to be revised. In addition to the latter, bulk fatigue data indicated that the reinforcing effect of nanoclays in PA6 (compounded or in-situ polymerized) is eventually lost in long-term fatigue straining regimes (ref. 2), a behavior that has not been observed in non-modified PA6. This loss of reinforcement indicates that the inhibition in viscoelastic deformation normally identified in this late fatigue straining regime can no longer occur. Related observations showed that concurrently with the previous, nucleation and growth of voids it is expected that the fatigue-related mechanism may become the principal mode of deformation. A clear link with this observation and the fracture behavior shift should be established. References: 1. S. C. Bellemare, M. N. Bureau, J. Denault and J. I. Dickson, Bulk Fatigue Damage Evolution in Polyamide-6 and Polyamide-6 Nanocomposites", Polymer Composites, vol. 26 (2005) 636-646. 2. M. N. Bureau, F. Glowacz and J. Denault, "Crack Propagation in Polyamide 6/Clay Nanocomposites", Annual Technical Conference ANTEC 2001 (SPE), May 6-10 2001, Dallas (USA) 2125-2129. Relationship between Project 7 TWA 22 and project 3 TWA 33 In July Dr. Michael Griepentrog (BAM) has had a full day meeting with Dr. Nigel Jennett (NPL) at BAM. During this meeting the interaction between Project 7 proposed in VAMAS TWA 22 and Project 3 proposed in TWA 33 has been discussed. Project 7 TWA 22 deals with the basic evaluation of dynamic indentation of polymers. There are no plans that this Project evaluates polymer nanocomposites PNC. In the current proposed Project 3 TWA 33, the focus is on the evaluation of the fracture mechanics of PNC. As a valuable tool to understand the mechanical properties of these materials, dynamic indentation will be used. It will complement the information obtained from Youngs modulus, yield strength and stress-strain behavior. However, there are only few publications on dynamic indentation of PNC and it is expected that some effort must be spent developing the methods for effectively performing dynamic indentation on these multiphase materials. This necessary work will be done in Project 3 TWA 33. To avoid duplication of efforts and to optimize the outcome of eventual parallel work on dynamic indentation, it was agreed by Dr. Michael Griepentrog (BAM) and Dr. Nigel Jennett (NPL) to have regular exchange of information and to coordinate the working plans. The possibility of a participation of Dr. Michael Griepentrog (BAM) into Project 7 TWA 22 was also discussed. The results reported by the Brazil group are being analyzed. It is noteworthy that the recent tests carried out by Dr. Michael Griepentrog at BAM resulted in fine tuning the indentation test protocol.
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6. Plan Initially the project will focus on neat PA-6 (UBE 1015B) and on PA-6 with 2 wt% organoclay commercially produced by Ube 1015C2 (natural clay) and Unitika M1030CH (synthetic clay), which offer a basis for comparison. The tests will include: (1) fracture mechanics (in a first round, fracture toughness, then in a second round fatigue crack propagation) of PNC including fractography; (2) nano-indentation; (3) analysis of suitability of dynamic tests as a replacement for large scale tensile tests. Testing protocols will propose methodology for specimen conditioning to ascertain specific humidity level of the samples. Dry-as-molded (DAM) or conditioned (24 hours at 50%RH/23C) will not suffice. In addition to standard quasi-static mechanical testing (tensile) required to perform LEFM measurements and test validity verifications, test protocol shall include required microstructural analysis to capture PNC main features (nano-filler dispersion, nanofiller intercalation/exfoliation, matrix crystallinity, etc.) using known techniques (TEM, XRD, etc.). Co-leaders (Volker Trappe from BAM and Martin Bureau from NRC are experts in the fracture mechanics and FCP of polymers and/or PNCs. M. Griepentrog will be the guiding expert for the nano-indentation tests. ISO 43 or ISO 17043 Statistical Techniques for Interlaboratory Studies will be followed. 7. Timescales Estimated time commitment per year, by a participant is: for test (1) 2-3 working days, for test (2) 2-3 working days and for test (3) is 3 working days Estimated date of planned start of project is within the first quarter of 2011. Estimated target date for completion of objectives and project is 4 years later. 8. International Participation and Industrial Interest Volker Trappe (BAM, Germany) Martin Bureau (NRCC/IMI, Canada) Michael Griepentrog (BAM, Germany) V. Silberschmidt (UK) G. Camino, Giulio Malucelli, Politechnico di Torino (Italy) M. Okamoto, S. Tanoue (Japan) T. Sakai can help us finding collaborators in Japan, but he will not be one

9. Funding / Other Resources There is no agreement for specific financial support.

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10. Deliverables and Dissemination VAMAS Technical Report (VTR) Publications in scientific journals and international nanocomposite congresses Communications and reporting to the ISO TC 229 aimed at development of ISO standard Communication and reporting to the ISO / TC 61 / SC 2 Communication and reporting to the ISO TC 164/SC 3

11. Date submitted Version of Wednesday, 15 September 2010, Martin Bureau, Volker Trappe & Michael Griepentrog

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