Polymer Nanoclay Composites
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About this ebook
There is a major lack of fundamental knowledge and understanding on the interaction between a filler and the polymer matrix. When it comes to nanoscale fillers, such as layered silicates, carbon nanotubes, graphene or cellulose nanofibers it is even more important to know accurate structure-property relationships as well as identifying the parameters influencing material behavior.
The reason for the lack of knowledge on how to process nanocomposites and why there are so few applications is that several scientific fields are affected and a joint effort of those scientific communities involved is necessary – starting from the filler manufacturing or pre-processing over polymer chemistry to the polymer processing.
In Polymer Nanoclay Composites, all involved scientific areas are viewed together for the first time, providing an all-embracing coverage of all stages of polymer clay nanocomposites processing from lab-scale to industrial scale – stages from the raw material over manufacturing of polymer clay nanocomposites to characterization and the final products.
Readers will gain insight in the physical/chemical pre-processing of layered silicates and their incorporation into a polymer matrix using sophisticated technologies (such as advanced compounding) as well as in real-time quality control of the nanocomposite production and future prospects. The book also describes nanotoxicological and nanosafety aspects.
- Covers the whole processing route with all aspects of the nanocomposites industry with particular focus on the processing of polymer clay nanocomposites
- Includes quality control and nanosafety
- Multidisciplinary approach from an industrial perspective
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Book preview
Polymer Nanoclay Composites - Stephan Laske
2004;45:7719–7727.
Chapter 1
Processing of calcium montmorillonites for use in polymers
Karl-Heinz Ohrdorf¹ and Helmut Flachberger², ¹Ingenieurbüro für Bentonit-Technologie, Wiesbaden, Germany, ²Montanuniversitaet Leoben, Department Mineral Resources and Petroleum Engineering, Chair of Mineral Processing, Leoben, Austria
Montmorillonites used as functional fillers in polymer compounds so far are based on natural sodium bentonites. It has been seen as a scientific challenge to process European calcium bentonites to comparable products. In order to exfoliate the calcium montmorillonite layer packages in a first step, a sophisticated technique was used to transform the calcium into sodium montmorillonite (alkaline activation). A new method to determine the necessary amount of sodium ions for that transformation has been developed and a Chemical Degree of Activation
as well as a Technical Degree of Activation
defined. Under the condition of both degrees at their optimum the second step, the organophile modification successfully has been completed with different reagents. Exfoliated montmorillonite platelets were detected by REM pictures. It could be shown that out of selected European calcium bentonite deposits nanofillers with even higher aspect ratios than in older publications reported can be achieved. Criteria for the selection of raw bentonites, the alkaline activation and the achievable aspect ratios have been proposed.
Keywords
Calcium montmorillonite; Chemical Degree of Activation; Technical Degree of Activation; achievable aspect ratio
Chapter Outline
1.1 Introduction 1
1.2 Definitions 5
1.3 Morphology of montmorillonite which is important for use in the polymer industry 5
1.4 Introduction—the activation of calcium bentonites to achieve a high aspect ratio 8
1.4.1 Problems in determining the soda ash dosage for the deposit-specific optimized cation exchange 9
1.4.2 Chemical–mineralogical basis of the alkaline activation of bentonites and technical problems in the realization 9
1.4.3 Thixotropy and yield point of bentonite suspensions 10
1.4.4 Definitions of a chemical and technical degree of activation 12
1.4.5 Activation technique 13
1.4.6 Determination of the yield point 16
1.5 Criteria for the selection of calcium bentonites, their alkaline activation, and the achievable aspect ratio 22
1.6 Conclusions 25
References 25
1.1 Introduction
There are currently countless publications dealing with the use of montmorillonite as a functional mineral filler in polymer compounds. The investigations which have been carried out have primarily used very well known, commercially available products like Nanofil and Cloisite (Rockwood Specialties, Inc.) but also less well-known products from Chinese producers.
These montmorillonite products, which are natural sodium montmorillonites, have all been modified to be organophile and made hydrophobic by various methods and using different reagents in order to achieve the necessary compatibility with the nonhydrophilic polymers. Although the manufacture of organophile derivates from alkaline-activated montmorillonite was already mentioned by Lagaly [1], it has not yet been taken over in industrial practice.
The exchange of sodium ions of the interlayers by cationic surfactants, especially primary, secondary, tertiary, and quaternary alkylammonium ions, lower the surface energy of the inorganic host and improve the wetting characteristics of the polymer matrix. In addition, the alkylammonium cations can provide functional groups that can react with the polymer matrix or in some cases initiate the polymerization of monomers to improve the strength of the interface between the inorganic and the polymer matrix [2].
One example of this is an overview of the alkylammonium surfactants and their use for the different polymers (Table 1.1).
Table 1.1
A Variety of Suitable and Proven Nanofil®-Qualities Are Available for a Lot of Polymers
Source: Company brochure of the former Süd Chemie AG.
There are, however, investigations which start with the assumption that certain surfactants negatively influence the mechanical and thermal properties of polymers and suggest for flame retardants the use of natural, non-organophile modified sodium bentonite which in poly 4,4′ diaminodiphenyl ether phenyl dichlorophosphate can be exfoliated very well [3].
Along with these organophile modified montmorillonites, acidic-activated montmorillonite has also been described as a new class of fillers, where, through the development of strong mineral acids which destroy the crystal structure of the montmorillonite, a silica structure results. Beyond that, even pure calcium montmorillonite has been suggested as a multipurpose filler [4].
The focus of the investigations lies both in the evaluation of the property changing qualities of the montmorillonite products in the polymer compounds and also in the understanding of the influence of the different reagents on the organophile modification of these [2].
There was no mention in these publications of the geology and genesis of the deposits, the mining and processing technology for the preparation of the montmorillonite products from the different raw bentonites. The organophile modification is generally referred to in the process steps of filtering,
drying,
and grinding
of the flocculating hydrophobic montmorillonite [5]; there is no clear allocation of causal relationships between the deposit-related morphology of the montmorillonite with regard to the targeted aspect ratio and the relevant application-related compound