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Abstract
A novel method was developed to allow the systematic design and selection of dispersants for mineral fillers and pigments in non-aqueous media such as polymers, coatings and lubricants. Dispersant probe molecules were varied systematically so that the effectiveness of the dispersant head and tail could be studied and optimised separately. Rheological tests on particle dispersions in a model fluid, squalane, were used to assess the effectiveness of each potential dispersant. Calcium carbonate, dolomite and silica were found to adsorb differing amounts of each probe molecule type. The relative affinity of each mineral for the various probe molecules could not be predicted or explained using Lewis acid-base concepts. The dispersant head group functionality was altered to suit the surface chemistry of the mineral whereas the dispersant tail was tuned to suit the dispersion medium. Using this approach we were able to identify highly effective dispersants for all minerals tested. Carboxylic acid, sulfonic acid, anhydride, amine and trichlorosilane were the most effective and versatile head groups found. The dispersant tail length and chemical composition were also varied. It was observed that the dispersion viscosity was lowered dramatically when the dispersant tail length was just two to three carbon atoms in length. No further decrease in viscosity occurred for dispersant tails up to twelve carbon atoms long. The chemical composition of the dispersant tail was also critical. A hydrocarbon tailed dispersant gave a much lower dispersion viscosity than did a similar dispersant with a less soluble, perfluoro tail. Our systematic method is generally applicable to selection and design of dispersants for minerals and pigments dispersed in organic media such as polymers, lubricants and coatings.
Introduction
Controlling the degree of particle dispersion is critical in many applications [1-3]. For example, pigments give much higher tinting strength when properly dispersed. In particulate-filled polymer composites good dispersion of the filler aids processing of the polymer melt [4,5] and gives composites with better mechanical properties, especially impact strength. Dispersants are a class of surfactants that are commonly employed to control the level of particle dispersion in a liquid dispersion medium. Particles tend to agglomerate due to the attractive van der Waals dispersion force that becomes very strong when particles approach each other closely. A dispersant acts by preventing particles from coming into close contact, thereby reducing the tendency towards particle agglomeration. Use of an effective dispersant can give viscosity reductions of several orders of magnitude (Figs. 2, 3 and 4). Thus, dispersants are often used to alter the rheological properties of commercial dispersions where appropriate dispersant selection and dosage level are often vital for successful product formulation. We describe a method that gives a systematic approach to dispersant selection. We used the method to find suitable dispersants for mineral fillers in polypropylene. However, we wish to emphasise that our approach is equally useful for dispersion of pigments and minerals in a wide range of different matrices.
Experimental Procedure
(1) Powders and Chemicals
The calcium carbonate studied was MicroXtra from Faxe Kalk (mean particle size 1.65m). Dolomite was Strdolomit A6 from Sala Mineral (previously Str Bruken) (70% < 10m, 35% < 5m). Silica was Microwhite B1 from Elkem. Chemicals were obtained from Aldrich and were used without further purification.
Systematic dispersant selection for minerals and pigments clear interpretation of adsorption data and consequently the use of a wholly aliphatic medium is recommended in the literature [21]. When a potential dispersant is added to the mineral dispersed in squalane it will only adsorb if there is a driving force for adsorption. It is entropically favourable for the dispersant to remain in solution and there must be some stronger, enthalpic interaction present if adorption is to occur. Thus, whenever adsorption takes place, we can deduce that there is some specific interaction between the head of the dispersant and some of the surface sites of that particular mineral. We have tested several different potential dispersants for each mineral, in each case the dispersant tail was kept constant, it was always a linear hydrocarbon chain, twelve carbons atoms in length. Whilst keeping the tail constant we varied the surfactant head to be one of a wide range of common organic functionalities, such as carboxylic acid, amine, alcohol, aldehyde, and ester groups. We added an excess of the additive (1.00 weight % versus filler), that is, much more than would be needed to form a close-packed monolayer. Then we measured the viscosity of the dispersion. Additives that did not adsorb gave little or no change in viscosity whilst additives that adsorbed in substantial amounts gave a large reduction in viscosity as compared to the dispersion containing no dispersant. The viscosity dropped by a factor of up to 104 or 105 for the dispersants adsorbing in the highest concentrations. Thus our rheological method was found to be extremely sensitive to dispersant adsorption. Using this system, we tested the effectiveness of several common head functionalities at adsorbing onto commercial samples of different mineral fillers. For each mineral we were able to compile a set of rheological curves that revealed the affinity of that particular mineral for each chemical type tested. It should be noted that the magnitude of the viscosity drop is related solely to the amount of surfactant adsorbed but not necessarily to the strength of the adsorption. We assumed that the viscosity drop per molecule of dispersant adsorbed is not dependent on the chemistry of the head group. That is, we assume that the same viscosity drop would result for adsorption of an equimolar amount of any of the different potential dispersants. Only the tail moiety contributes to dispersion as the head of an adsorbed molecule is not in contact with the solvent. Because the surfactant tail structure is held constant, we can directly compare the relative amount of each potential dispersant that adsorbed onto a given mineral. The results were plotted in the conventional way for such data, that is, on a log-log scale of complex viscosity * versus shear rate. By examination of the rheological results it is possible to make several important conclusions. As stated previously, the method was found to be extremely sensitive. Using just 20 weight % of filler, the measured viscosity drop upon dispersant addition was typically 103 for the better dispersants. It is therefore possible to detect very small differences in the amount of additive adsorbed. Another, key observation is that no two minerals displayed the same surface chemistry, the relative affinity of each mineral towards the various chemical types was unique. For each mineral, we have identified one or more suitable dispersant head group chemistries. Calcium carbonate, (CaCO3) and dolomite (CaCO3.MgCO3) are similar chemically and are often therefore assumed to behave in the same manner with respect to additive adsorption [9]. Our tests showed that, in fact, even these two chemically similar minerals displayed noticeably different surface chemistry. In particular, for dolomite the strong, sulfonic acid adsorbed to the greatest extent followed by the carboxylic acid, then the silane, the acid anhydride and the amine (Fig. 1).
Figure 1 Rheological screening of 16.7 weight % Calcium carbonate in Squalane and addition of 1 weight % probe molecule relative to filler. The probe molecules are: base system (no probe molecule), 1-dodecanol, dodecylbenzenesulfonic acid, dodecyltrichlorosilane, dodecylamine, dodecanoic acid, and 2-dodecen-1-ylsuccinic anhydride.
Whereas for calcium carbonate, the acid anhydride was adsorbed in the highest amount followed by the acid, then the amine, the silane and lastly the sulfonic acid (Fig. 2). It can be concluded that the acid anhydride and carboxylic acid head groups are the best choices for calcium carbonate. For dolomite the sulfonic acid and carboxylic acid are the two best choices. As expected, these acidic test molecules are able to adsorb in high concentrations to the basic mineral. Somewhat surprisingly, the basic, amine probe molecule also adsorbed in a very high concentration onto these two basic minerals. The data shows that it is not possible to predict the relative adsorbed amounts of different head groups based on Lewis acid-base concepts. If the best dispersant head group is needed, then it is essential to actually measure the amount of each additive type adsorbed as we have done here. Silica is known to be predominantly acidic at the surface [22,24] and so it is expected that silica should have a markedly different surface chemistry than the two basic minerals. For silica, the silane was the best treatment by a clear margin.
Figure 2 Rheological screening of 16.7 weight % Dolomite in Squalane and addition of 1 weight % probe molecule relative to filler. The probe molecules are: base system (no probe molecule), 1dodecanol, dodecylamine, 2-dodecen-1-ylsuccinic anhydride, dodecyltrichlorosilane, dodecanoic acid, and dodecylbenzenesulfonic acid.
That was not unexpected because the standard surface treatments for (silica) glass fibres are silanes which are well known to form strong, covalent bonds to silanol groups on the silica surface [22]. Furthermore, it has been shown that trichlorosilanes are especially reactive towards the different types of silanol groups present on silica [22]. After the silane, the sulfonic acid and the acid anhydride were the next best treatments followed by the amine and then the carboxylic acid (Fig. 3). Thus, the silica did have a significantly different surface chemistry than the two basic minerals but again, the surface was amphoteric in nature, adsorbing significant concentrations of both acidic and basic probe molecules. It could be argued that the results seen in this study are different from other studies because of trace impurities in the fillers used. The minerals in this study are commercial products and not totally pure materials. We recognise that even though the samples used here are chemically pure, even small levels of impurity on the surface may significantly alter the results affinity of the dispersants. In practice, totally pure minerals are not used commercially to any great extent, due to their prohibitively high cost. As commercial materials all have some level of impurity likely to affect the surface properties, it makes sense to measure the behaviour of the precise material grade of interest rather than relying on generic data from other sources. 6
Figure 3 Rheological screening of 16.7 weight % Silica in Squalane and addition of 1 weight % probe molecule relative to filler. The probe molecules are: base system (no probe molecule), 1dodecanol, dodecanoic acid, dodecylamine, 2-dodecen-1-ylsuccinic anhydride, dodecylbenzenesulfonic acid, and dodecyltrichlorosilane.
Aside from allowing us to identify suitable head / anchor groups for dispersants, this test also gives information that can be useful in other ways. For example, using the results from the rheological test it is possible to predict whether other additives in a specific formulation are likely to adsorb onto a given mineral. Simply examining the chemical structure of an additive will show if it contains functional groups that could potentially cause it to adsorb to the mineral in question. Additives with the potential to adsorb include antioxidants in filled polymers or catalysts used to cure coatings. Another use for the adsorption data is in predicting and understanding adhesion between the filler and the polymer matrix [23,24]. If the polymer contains functional groups that are able to adsorb onto the mineral then it is anticipated that adhesion would be increased by any such polymer-filler interactions [23,24]. Naturally, in both of these cases, steric factors must also be considered when attempting to predict the feasibility of adsorption for a certain functional group within a molecule. The rheological test proved to be an extremely effective and sensitive way of indirectly determining two important parameters. It was of utility both for studying additive adsorption and for directly measuring the viscosity drop caused by the improvement in the dispersion of the 7
Systematic dispersant selection for minerals and pigments particles. We found that each mineral displayed its own unique surface chemistry and were able to identify an effective dispersant head moiety to anchor dispersant molecules onto each mineral. We therefore believe that this technique is suitable for the systematic development of new, improved dispersants in the future.
Tail Length
Steric stabilisation relies on the dispersant to prevent the close approach of particles. If the particles are allowed to approach each other too closely then the attractive Van der Waals forces, which dominate over short distances will cause strong particle agglomeration. Therefore, in order to be effective, the steric layer created by the dispersant must be thick enough to keep the particles separated by a sufficient distance. The required thickness of the steric layer will depend upon the magnitude of the attractive forces between the particles these, in turn, are dependent upon the Hamaker constant of the dispersed material in the dispersion medium [28,29]. Our results are therefore only quantitatively valid for the dispersion of calcium carbonate in squalane. Minerals and pigments dispersed in other hydrocarbon liquids are expected to behave somewhat differently [16,28,29] although our results should remain qualitatively valid to those systems. If one wishes to find the optimal dispersant for a mineral in a more polar medium, e.g. PVC, nylon, polyester etc., then it would be appropriate to choose a model fluid other than squalane to more closely matching the solubility parameter and Lewis acid-base characteristics of the more polar medium.
Figure 4 Effect of probe tail length on dispersant efficiency, * obtained from rheological screening at frequencies of 1 Hz, 2 Hz, 3 Hz.
We measured the viscosity of calcium carbonate in squalane with different dispersants added (Fig. 4). The dispersants chosen were a homologous series of carboxylic acids, each dispersant had a linear hydrocarbon tail of different length. Excess dispersant was used in all cases so we were able to measure the effectiveness of the dispersants. Effectiveness has been defined as the maximum effect achievable using a given surfactant when excess is present [30]. The use of a dispersant with only a two carbon tail was sufficient to reduce the dispersion viscosity * (as measured at 3 Hz) by almost two orders of magnitude (Fig. 4). A greater drop in viscosity was achieved using the analogous dispersant with a three carbon tail. It was interesting to note that further lengthening of the dispersant tail did not give a further drop in viscosity. Thus, the use of a longer dispersant tail does not give any noticeable advantage. As mentioned previously, the industry standard dispersant for calcium carbonate in PP is stearic acid, which is eighteen carbons in length. According to our results, a similar degree of dispersion could be attained using a much shorter dispersant tail. It should be mentioned that our work here is performed on dispersants that are so-called semi-steric stabilisers. These short chain dispersants enhance the degree of dispersion considerably but the molecules are too short to completely prevent agglomeration. This can be seen in our results where the slope seen for each plot is indicative of non-Newtonian behaviour caused by agglomeration. Longer chain, oligomeric and polymeric steric stabilisers often much more effective leading to a more Newtonian response. 9
Systematic dispersant selection for minerals and pigments Unfortunately, it was not possible to obtain longer, polymeric molecules in the same homologous series for our studies.
Figure 5 Effect of probe tail chemical composition on dispersant efficiency (16.7 weight % Calcium carbonate in Squalane and addition of 1 weight % to filler of probe molecule.) The probe molecules are: base system (no probe molecule), perfluorododecanoic acid, and dodecanoic acid.
The fluorocarbon tail however gives much poorer dispersion. Whilst the fluorocarbon tail is somewhat effective, it only gives a drop in viscosity of 10 fold compared to the viscosity with no dispersant added whereas the hydrocarbon tailed dispersant gives a 1000 fold drop in viscosity. 10
Systematic dispersant selection for minerals and pigments These results illustrate that it is vital to choose a dispersant with the correct tail in terms of chemical composition. It is well known that fluorocarbons have very poor solubility in hydrocarbons and this is why the perfluoro dispersant is so poor in this case. Thus, matching the solubility of the tail to the polarity of the dispersion medium is of paramount importance if effective dispersion is required.
Conclusions
Dispersants are a class of surfactant used in many industries world-wide. The correct choice of dispersant is vital in countless applications for controlling both the level of particle dispersion and for tuning the viscosity of such dispersions. Despite the importance of dispersants, there has not previously been a good way to systematically choose the correct dispersant, nor to design new, better dispersants. We have developed a systematic, rheologically based methodology that clearly shows the relationship between dispersant structure and effectiveness. The dispersants were viewed as a surfactant containing a head / anchor group and a tail moiety, each of these two portions were varied and optimised separately. The chemistry of the head was selected to be one that bonded in high concentrations to the mineral particles. It was found that the optimal choice of head group is individual for each mineral depending upon the surface chemistry of that mineral and that no two minerals showed the same adsorption behaviour. The optimal structure of the dispersant tail was chosen so that it would sufficient length and solubility in the dispersion medium. The chemical composition and length of the tail were found to dramatically affect the effectiveness of the dispersants in terms of lowering the viscosity of the mineral dispersions. Specifically, the tail was more effective when it was similar in chemical composition to the dispersion medium. The length of the tail was also seen to be very important. The viscosity of the dispersion was lowered as the dispersant tail moiety was increased up to three carbons in length. Further increase in the carbon tail length up to twelve carbons had virtually no further impact on dispersion viscosity. By varying the two parts of the dispersant separately we were able to identify very effective dispersants for each mineral dispersed in a non-polar aliphatic hydrocarbon liquid medium. This study has highlighted some of the main parameters determining the effectiveness of dispersants. It also provides a way to choose dispersants from sets of existing chemicals as well as insight into how new, improved dispersants and coupling agents for minerals and pigments can be designed. We performed this study using a rheometer for the viscosity measurements, however, we wish to emphasise that qualitatively similar results can be obtained using much less expensive equipment. A flow cup, DIN cup, or ISO cup as commonly used in industry, can be used instead of a rheometer, to measure relative viscosity more quickly and cheaply. We therefore anticipate that our method will be of value in academia and in industry for improved surface treatment of particles in applications including nanocomposites, flame-retardant-filled polymers, polymer composites, coatings, lubricants and other particulate-filled systems.
Acknowledgements
We sincerely thank Borealis AB, Borealis Oy, MinFo, Faxe Kalk, Finnminerals Oy, Kemira Oy, Str Bruken AB, Aros Mineral AB, Akzo Nobel Surface Chemistry AB, Lax Bruks AB, Elkem AS and NUTEK for funding this work and for valuable input.
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