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The rotational molecular dynamics of water confined to layered oxide materials with brucite structure was studied by dielectric spectroscopy in the frequency range from 10(-2) to 10(7) Hz and in a broad temperature interval. The layered double hydroxide samples show one relaxation process, which was assigned to fluctuations of water molecules forming a layer, strongly adsorbed to the oxide surface. The temperature dependence of the relaxation rates has an unusual saddlelike shape characterized by a maximum. The model of Ryabov et al. (J. Phys. Chem. B 2001, 105, 1845) recently applied to describe the dynamics of water molecules in porous glasses is employed also for the layered materials. This model assumes two competing effects: rotational fluctuations of water molecules that take place simultaneously with defect formation, allowing the creation of free volume necessary for reorientation. The activation energy of rotational fluctuations, the energy of defect formation, a pre-exponential factor, and the defect concentration are obtained as main parameters from a fit of this model to the data. The values of these parameters were compared with those found for water confined to nanoporous molecular sieves, porous glasses, or bulk ice. Several correlations were discussed in detail, such as the lower the value of the energy of defect formation, the higher the number of defects. The pre-exponential factor increases with increasing activation energy, as an expression of the compensation law, and indicates the cooperative nature of the motional process. The involvement of the surface OH groups and of the oxygen atoms of the interlayer anions in the formation of hydrogen bonds was further discussed. For the birnessite sample, the relaxation processes are probably overlaid by a dominating conductivity contribution, which is analyzed in its frequency and temperature dependence. It is found that the conductivity of birnessite obeys the characteristics of semiconducting disordered materials. Especially the Barton/Nakajima/Namikawa relationship is fulfilled. Analyzing the temperature dependence of the direct current (dc) conductivity sigma0 in detail gives some hint that sigma0(T) has also an unusual saddlelike form.
"17. A production process for a water-absorbent resin powder, which comprises the steps of: polymerizing an aqueous monomer solution containing a monomer and a crosslinking agent; heat-drying the resultant crosslinked hydrogel polymer; and pulverizing the resultant dry polymer; wherein:
the step of pulverizing the dry polymer is carried out so as to form a water-absorbent resin powder having a bulk-density, as measured by an apparatus according to JIS K-3362, of not less than 0.65 g/ml;
- Claim 1 of auxiliary request 16 involved an inventive step even if D4 was considered to represent the closest prior art. There was clearly no hint in the art to adjust the bulk density of the powder to not less than 0.65 g/ml in order to improve the absorption capacity under load, irrespective of whether (i) the preparation of the hydrogel polymer by polymerising an aqueous monomer solution containing a monomer and a crosslinking agent, (ii) the combination of the drying step with a forcible cooling step and (iii) the surface-crosslinking of the powder could be considered obvious in view of D1. The relation between bulk density and absorption capacity under load was illustrated in table 2 of the patent in suit, in particular examples 10-13, 6, 15, 16, 19-21. Not only did these examples show the presence of such a relation, they also showed that this correlation was present within the entire useful range of the powder particle diameter, namely between 150 and 850 mym.
- The argument of the opponent, that the relation between the increase of bulk density and the improvement of absorption capacity under load was foreseeable for the skilled person, was a mere allegation which was not based on any technical evidence. Also the argument that there was no relation between bulk density and absorption capacity under load was not credible in the absence of technical evidence. In fact, the opponent did not submit any technical evidence to show that water-absorbent resin powder with a bulk density of less than 0.65 g/ml (i.e., outside the claimed scope) showed an absorption capacity under load comparable or superior to that with a bulk density of not less than 0.65 g/ml.
- Regarding the missing feature concerning the bulk density of the water-absorbent resin powder of not less than 0.65 g/ml, it was a feature which was adjusted automatically by the forcible cooling. Anyway, the bulk density was not a feature which could be considered independently from the forcible cooling. This was acknowledged in the patent in suit (see paragraph [0072]).
- D7 could also be considered to represent the closest state of the art since it disclosed in example 1 a process for the preparation of a water-absorbent resin powder comprising the steps of polymerizing an aqueous monomer solution containing a monomer and a crosslinking agent, heat-drying the resultant crosslinked hydrogel polymer at an air temperature of 180C, forcibly cooling the dry polymer at 60C, pulverizing the resultant dry polymer and screening it to a particle size between 120 - 850 mym. The bulk density was a feature which was adjusted by the forcible cooling and the surface-crosslinking was a conventional measure obvious to the skilled person.
- the pulverizing of the dry polymer is carried out so as to form a water-absorbent resin powder having a bulk density, as measured by an apparatus according to JIS K-3362, of not larger than 0.65 g/ml, and
Table 2 shows that by adjusting the bulk density of a cooled water-absorbent resin powder so that it is not less than 0.65 g/ml (see examples 10, 12, 6, 15, 16 and 19-21 according to the invention as listed in table 2 which have a bulk density of 0.74, 0.76, 0.67 and 0.68 g/ml) the absorption capacity under load, in particular under a load of 4.90 kPa, is improved (it ranges between 24-28 g/g).
3.3.1 The skilled person starting from the production process for a water-absorbent resin powder of D4 and aiming at the provision of production process of an improved product would not find any hint in the art that the dry polymer, after the forcible cooling, should be pulverized in such a manner that the powder has a bulk density of not less than 0.65 g/ml. Furthermore, the opponent has not shown that such a pulverizing step belongs to the general background knowledge of the skilled person.
"1. A process for the preparation of a granular detergent composition or component having a bulk density of at least 650 g/litre, which process includes the step of neutralising a liquid acid precursor of an anionic surfactant with a solid water-soluble alkaline inorganic material, the process being characterised by the steps of:
(ii) gradually adding the acid precursor to the high-speed mixer/granulator while maintaining a temperature not higher than 55 C, whereby neutralisation of the acid precursor by the water-soluble alkaline inorganic material occurs while the mixture remains in particulate form;
(iii) granulating the mixture in the high-speed mixer/granulator, in the presence of a liquid binder, whereby a granular detergent composition or component having a bulk density of at least 650 g/litre is formed."
- The goal of the patent in suit was to obtain a non-sticky, free-flowing powder detergent, being of granular form and having a certain particle size limitation. The skilled person considering document (1B) would not replace tripolyphosphate with zeolite because that document taught to keep the water content low in order to avoid, for example, tackiness and lumping (page 4, lines 84 to 90); zeolite comprising bound water would release water when the temperature is increased. The temperature reached by the process according to document (1B) was between 50 to 110C or even higher (page 1, lines 76 to 80), whereas the patent in suit required a temperature below 55C. An amount of 3 to 8 wt% of binder, in particular of water, was a specific amount allowing the goal set in the patent in suit to be rached (letter of 8. June 1998, page 2 and paragraph bridging pages 5 and 6).
Fortunately, they had a hose attached to a wand that was held by a clasp on a pole and that hinted that it might be a movable water delivery device. Close examination of the wand showed that there were a couple of rows of holes that might be designed to extrude water. Except there was nothing on the wand to indicate how to activate it. 041b061a72