Membranes silicone rubber

Figure 9.5 Pervaporation separation of acetone-water mixtures achieved with a water-selective membrane poly(vinyl alcohol) (PVA), and an acetone-selective membrane (silicone rubber) [21]. Reprinted from Hollein et al. [21], p. 1051 by courtesy of Marcel Dekker, Inc.

C02-permeable membrane (silicone rubber) Cuvet Glass window... 

Membrane (Silicone rubber with silver halide)... 

Figure 6.31. Experimental data for the effect of downstream pressure on pervaporation. (Upstream pressure, 10,325 Pa temperature, 23 C membrane, silicone rubber system, water/eihanol mixtures.) (Reproduced from [240] with permission.)...

In heterogeneous solid membranes, the active (selective) material is mixed in the form of a powder with a suitable binder (e.g., silicone rubber) and cast in the form of thin membranes. In this case, the difficulties associated with single-crystal fabrication are avoided, and better stability is obtained than in membranes compressed from polycrystalline powder. 

Simple encapsulation or dispersion of neutral carriers in silicone rubber is an easy way to fabricate silicone-rubber ion-sensing membranes based on neutral carriers. 

However, there seems to be some drawback in the solubility or dispersibility of ion-sensing material in silicone rubber. This is mainly because silicone rubber does not contain a large quantity of plasticizer as the membrane solvent, in which neutral carriers can be dissolved easily, unlike in plasticized-PVC ion-sensing membranes. This issue is serious, especially with silicone-rubber membranes containing neutral carriers that show high crystallinity. Valinomycin, a typical ionophore, seems applicable to silicone-rubber-based K" -selec-tive electrodes [7,8,12-14]. Conventional crown-ether-based neutral carriers are also quite soluble in silicone rubber. 

The highly dispersible calix[4]arene neutral carriers can also improve the durability for neutral-carrier-type ion sensors. Time-course changes in both sensitivity (slope for Na+ calibration graph) and selectivity (selectivity coefficient for Na" " with respect to K+) were followed in the Na -ISFETs based on ion-sensing membranes of silicone rubber-(l), plasticized PVC-(l), and plasticized PVC-(2) (Fig. 2). Deterioration proceeded quite quickly in the Na -ISFETs of plasticized PVC-(2) both the Na+ sensitivity and selectivity... 

FIG. 3 Comparison of membrane impedance among silicone-rubber-based ion-sensing membrane containing calixarene neutral carriers (5) (0) (6) ( ) and (2) (A)- (From Ref. 21.)... 

FIG. 4 Selectivity comparison among silicone-rubber-membrane Na -ISFETs based on calixarene neutral carriers (1), (2), and (5). 

FIG. 6 Time-course changes of potential response for silicone-rubber-membrane Na+-selective electrodes based on neutral carriers (5), (2), and bis(12-crown-4) on changing Na concentration from 1 X 10 to 3 X 10 M. (From Ref. 22.)... 

Foly(dimethylsiloxane) (silicone rubber) membranes are fabricated by hydrolysis of alkox-ysilyl terminal groups of silicone-rubber precursors [oligo(dimethylsiloxane) derivatives and crosslinking agents], followed by condensation. Covalent bonding of neutral carriers carrying an alkoxysilyl group to silicone rubber is, therefore, feasible by simple reaction of the silicone-rubber precursor with alkoxysilylated neutral carriers, as schematically shown in Scheme 1 [44]. 

As neutral carriers for the chemical modification, 16-crown-5 and calix[4]arene derivatives possessing a triethoxysilyl group (7) and (8) were designed for Na sensors. Triethoxysilylethyl-16-crown-5(7) was then mixed with a silicone-rubber precursor for the membrane fabrication accompanying covalent bonding of the neutral carrier. Comparison of IR spectra before and after extraction of the nonbonded neutral carrier... 

SCHEME 1 Mechanism for chemical modification of poly(dimethysiloxane) (silicone rubber) membranes with ion-sensing active material. 

FIG. 11 Potential response of Na+-selective electrodes based on silicone-rubber membranes modified chemically by triethoxysilylated calix[4]arene (8) (O) without anion excluder ( ) with TFPB ( ) modified chemically by triethoxysilylated tetraphenylborate (9) as well. (From Ref. 44.)... 

Applicability in biological ion assay is an important factor for biocompatible potentio-metric ion sensors. Attempts were made to determine Na" " concentrations in human blood sera by using silicone-rubber membrane Na+-ISFETs based on (5) [Fig. 17(a)] [29]. The found values for Na concentration in undiluted, 10-fold diluted, and 100-fold diluted serum samples are in good agreement with the Na" " calibration plots. Even in the undiluted serum samples, only a slight potential shift was observed from the calibration. This indicates that the calixarene-based silicone-rubber-membrane Na+-ISFETs are reliable on serum Na assay. For comparison with the silicone-rubber membrane, Na -ISFETs with corresponding plasticized-PVC membrane containing (2) or (5) were also tested for the Na assay. The found values of Na" " concentration... 

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