The effect of fumed silica in RTV-1 silicone rubber sealants

by H. Cochrane and C.S. Lin, CAB-O-SIL Division, Cabot Corporation, Tuscola, IL

Reprinted from the August 1985 issue of Rubber World Reprinted with the permission of Rubber World magazine

Introduction

Since their development 20 years ago1,2, one component silicone rubber sealants (RTV- 1 ) have become one of the most versatile and widely used high performance sealants in both the home and in industry. Their uses range from caulking bathroom tile, sealants for glazing glass skyscrapers, to formed-in-place gaskets for automobiles and sealing and bonding applications in the Space Shuttle Orbiter. This increased demand for silicone sealants has resulted in the rapid growth in the number of silicone sealant manufacturers in the USA during the last five years.

Experimental Filler and filler properties

The hydrophilic fumed silicas used in this study are commercial materials produced by our company. The series of hydrophobic fumed silicas were experimental samples. The precipitated silicas studied for comparative purposes are commercially available products. The silicas were characterized by measuring the following analytical properties: surface area, pH, moisture level and pour density values. The treatment levels of the hydrophobic silicas were estimated from their carbon contents. Surface areas of the silicas were determined by nitrogen adsorption at -- 196C using a single point B.E.T. method 9. The pH values were determined for 4 weight % aqueous slurries using a pH meter. In the case of the hydrophobic silicas the water was replaced with a 80/20 volume mixture of isopropanol and water. The hydrophilic fumed silicas all had similar pH values in the range of 4.1-4,3. The hydrophobic silicas had similar values in the range of 5.4- 5.9 and the precipitated silicas had values in the range of 7.0-8.0. The moisture contents of the silicas were determined by measuring their weight losses after heating in an oven for 2 hours at 105C. The pour densities of the silicas were determined by pouring the silica into a calibrated vessel. After allowing the material to settle for 5 minutes, the pour density was calculated by dividing the sample weight by its volume. The pour densities of all of the undensed hydrophilic silicas were similar and <50 g/1.

RTV- 1 silicone sealants have many desirable properties, being a one component system which can cure at ambient temperature and humidity. They have good theological and cured physical properties, including self-adhesive properties and excellent clarity. In addition, the sealants show good low and high temperature resistance, excellent weatherability, ozone and chemical resistance. This combination of rather unique properties is related primarily to the three major components in the sealant, the silicone polymer, the silicone crosslinker system and the reinforcing filler, normally fumed silica.

Due to the very proprietary nature of the sealant technology, rather limited information has been published outside the patent literature on these products. Although several articles have been published on the chemistry, crosslinking mechanism and properties, 3-7virtually no information has been published on the influence of the fumed silica filler on the ease of compounding, theological and cured physical properties of the sealants. Lippe8 studied the rheological properties of several sealants including a silicone rubber sealant. In that paper he described a rapid test method for the determination of their yield stress value, viscosity and degree of pseudoplasticity. He showed that these parameters can be useful in predicting slump resistance and extrudability of sealants.

Polymers and other ingredients

The silicone polymers used in this work consisted of a 18 Pa.s, hydroxy terminated polydimethylsiloxane (Baysilone* Polymer E-18) and a 1 Pa.s polydimethylsiloxane (Baysilone M-1000) which was used as a non-reactive diluent. A 50/50 weight blend of methyltriacetoxysilane and ethyltriacetoxy silane (Baysilone Crosslinking Agent 3187) was used as a crosslinker. A trace amount of dibutyltindilaurate catalyst was used to control the cure rate.

The purpose of this article is to examine how variations in the properties of the fumed silica fillers can affect the compounding, theological and cured physical properties of silicone sealants. These properties include moisture content, bulk density, surface area, loading and surface treatment level. The silicone sealant manufacturer is specifically concerned with how variations in these properties will affect the rate of incorporation, ease of dispersion, slump resistance, extrusion rate and cured physical properties, especially tear resistance and compound clarity.

Formulation and compounding conditions

In addition, it was hoped to derive a better basic understanding of how interactions between the silica and the polymer and crosslinker affect the rheology and cured physical properties of the sealant. This would be useful in developing an optimized silica for the sealant. A cone and plate viscometer was used throughout the evaluation to provide a better measure of which filler properties affect the rheology of sealants.

The compounding was carried out in a Drais 1.5 liter laboratory size planetary mixer. The standard formulation consisted of 100 parts by weight of 18 Pas silicone polymer, 50 parts of 1 Pas non-reactive diluent, 7 parts of the alkyltriacetoxysilane mixture, 14 parts of silica filler and 0.03 parts of the tin catalyst. All the silicas were pre-dried to less than 0.5 wt. % moisture level prior to compounding in order to prevent premature cure or gel formation in the sealant. It was especially important to dry the precipitated silicas which contained moisture levels between 4 to 8 wt. %. In contrast, the fumed silicas moisture values were normally <1 wt. %. The polymer and diluent were initially mixed for 15 minutes at 50 rpm under vacuum. The crosslinker was then added and the sealant was allowed to mix with a nitrogen sweep for a further 15 minutes. Silicas were introduced at this point and the incorporation time was
1

recorded for each run. The catalyst was added last and mixed for 30 more minutes under nitrogen to achieve good silica dispersion. A vacuum was then drawn during a final mix period of 15 minutes.
Theological.measurements

Table 1 effect of reinforcing filler and crossIinker level

Formulation 1 2 5 6

The viscosity data and yield stress values in this study were obtained with a Haake Rotovisco rotating viscometer, model RV3, operating in the cone and plate sensing mode. A Hewlett-Packard XYT recorder was used in conjunction with the viscometer. Samples were evaluated at shear rates of up to 175 reciprocal seconds with an acceleration of 17.5 reciprocal seconds per minute. The shear thinning indices (STI) were the ratio of viscosity obtained at 17.5 s -l*(at 1 rpm) to the viscosity obtained at 87.5 S-l (at 5 rpm). Slump was measured according to ASTM Designation D-2202. Extrusion rate was measured using MIL-Specification 7502 which specified extrusion through a 3.17 mm diameter nozzle. Rates were determined over the pressure range from 0.14 MPa to 0.41 MPa. Penetration data were obtained using the SUR penetrometer, model PNR 6. It is a solenoid controlled, electronically timed, falling rod and needle type apparatus used to measure the consistency of the sealants. The depth the needle penetrated into the sealant (in 0.1 mm units) after 1 second was recorded for most of the sealants. For the very flowable sealants a shorter time period of 0.1 second was used.
Curing properties

o < - - 1 4 - - > Fumed silica 136 m2/g (parts) 12 2 7 6 (parts) Crosslinker level Processing and theological properties 19 24 12 (min) o Incorporation time good <--Excellent--> Dispersion level 11 17 10 24 (rein) Skin time o 0 500 540 (Pa) Yield value 81.2 193 575 670 (Pas) Viscosity, 1 rpm 2.6 13 21 1.9 STI >5 0 0 >>5 (cm) Slump value 140 110 (0.1 mm) Very high Penetration value 110 100 120 Extrusion rate,0.28 MPa (g/min) Cured-physical properties 21 7 15 21 Shore A durometer (kNm -1) 12 42 51 5.6 Die B tear -l (kNm ) ~O 1.4 17 Peel adhesion 0.21 0.32 034 (MPa) 013 Modulus, 50% 1 28 1 41 1 51 (MPs) 0.32 Tensile 1 68 1 03 (MPa) Lap shear 420 440 330 460 Elongation at break (%) 78 46 54 43 Clarity (% T at 500 nm)

the crosslinker level and order of addition of the silica. The remaining tables show the effects of variation in fumed silica moisture level, bulk density, surface area, the effect of silica surface pretreatment level and finally the effect of substitution of an alternate filler, precipitated silicas.
Crosslinker level

An approximate indication of the rate of cure of the sealant was measured using the skin time test. In this test the time taken for the sealant surface to become tack free to the touch is recorded. The rate of cure is dependent on the relative humidity and temperature. In these studies the sealant samples were cured at ~ 23C and at a relative humidity of 30-50%.
Cured physical properties

After the samples had been cured 7 days at ambient temperature, their cured physical properties were measured, using a Monsanto Tensometer 500 (crosshead speed of 0.508 m/min). Tensile strength, elongation and modulus values were measured according to ASTM D-412. Die B tear strength was determined per ASTM D-624 and Shore A hardness per ASTM D-2240. The adhesion-in-peel test was performed largely in accordance with ASTM Designation C-794. The peel strength properties of the cured sealants were evaluated using glass plates. All specimens were allowed to cure at least 5 days at ambient temperature before the test. The strength test of adhesive bonds in shear by tension loading (metal-to-metal) was carried out according to ASTM D-1002. The preparation of the aluminum substrate was described in detail in ASTM D-2651. The clarity values were generated by using a Bausch and Lomb Spectronic 88 spectrophotometer. This is a single beam, grating instrument which provides direct readout of percent transmittance at a given wavelength. For ease of comparison a wavelength of 500 nm was chosen.
Results and discussion

The poor theological and cured physical properties of an RTV- 1 formulation containing no fumed silica are shown in formulation 1, table 1. The remainder of the results in table 1 show the effect of increasing the crosslinker level (MTAS/ETAS blend) from 2 to 12 parts. At a level of 2 parts the formulation had very poor slump properties (>5cm) and moderate cured physical properties. As the crosslinker level was increased from 2 to 12 parts the rheological properties of the formulations changed, with a general increase in yield stress value and viscosity and with decreases in penetration and extrusion rate values. Above a level of 2 parts the cured physical properties were fairly constant. Based on these results a crosslinker level of 7 parts was chosen for all subsequent studies.
Table 2 effect of order of fumed silica addition
Formulation 1 3 5

Fumed silica 136 m2/g Order of addition

(parts) (1) (2) (3)

SiO 2 XL

14 1/2SiIO2 XL 1/2SiO2

XL SiO2

Processing and theological properties Incorporation time (mm)

Dispersion level Skin time Yield value Viscoslty, 1 rpm STI Slump value Penetration value Extrusion rate, 0.28 MPa Cured physical properties Shore A durometer Die B tear Peel adhesion Modulus, 500/0 Tensile Lap shear Elongation at break Clarity (% T at 500 nm) XL = crosslinker

(mm) (Pa) (Pa s) (cm) (0.1 mm) (g/min) (kNm -1) (kNm -l) (MPa) (MPa) (MPa) (%)

12 small gels 15 320 41.2 1.1 0 230 170 19 5.1 2.1 0.30 1.6 2.4 430 62

12 14 Excellent 20 12 460 560 63.1 65.3 2.0 21 0 0 170 180 140 110 21 4.9 1.1 0.32 1.5 1.5 420 59 20 5.1 1.3 0.30 1.4 1.0 460 57

The results of this extensive study are shown in tables 1 through 7. The first two tables show the effect of varying
2

Table 3 effect of adsorbed moisture level on the fumed silica

Formulation 1 2 3 4

Table 4 effect of fumed silica bulk density

Formulation 2 2 Surface area 136 143 (m /g) Density (g/l ) 85 Processing and theological properties Incorporation time (min) 14 6 Dispersion level excellent poor Skin time (min) 12 30 Yield value (Pa) 560 290 Viscosity, 1 rpm (Pa.s) 65.3 42.1 STI 2.1 1.3 Slump value (cm) 0 0 3 192 4 199 84

Fumed silica 136 m2/g Wt. % moisture Dispersion level Skin time
Yield value Viscosity, 1 rpm STI Slump value

50

(parts)

< - - - - 1 4 - - - - > 0.50 1.03 2.25 3.03 13 14 <---- Excellent----> 26 15 21

450 64.0 1.9 0 150 120 470 64.8 1.9 0 150 110

Processing and rheological properties incorporation time (rein) 15

(mm)
(Pa) (Pas) (cm)

14 large gels 25
610 66.6 1.9 0 120 120

480 62.3 1.9

10 8 excellent grainy 24 27 490 700 51.5 81.6 1.3 2.5 0 0

Penetration value (0.1mm) Extrusion rate, 0.28 MPa (g/min)

Cured physical properties Shore A durometer

160 110

210 230

110 60

220 140

Penetration value (0.1 mm) 160 Extrusion rate, 0.28 MPa (g/mm) 140
Cured physlcal properties

Shore A durometer 18 20 21 18 Die B tear (kNm-1 ) 5.1 5.1 4.9 5.1 -l Peel adhesion (kNm ) 1.1 1.4 1.0 1.1 Modulus, 50% (MPa) 0.31 0.33 0.30 030 Tensile 1.6 (MPa) 1.7 1.5 1.2 Lap shear 1.4 (MPa) 1.3 1.7 11 Elongation at, break 450 (%) 440 390 460 Clarity (% T at 500 nm) 61 58 59 58 Rheological properties after 4 months aging Yield value (Pa) 450 570 560 720 Viscosity, 1 rpm (Pas) 55.0 58.4 60.5 58.4 STI 2.0 2.1 1.9 1.7

Die B tear Peel adhesion Modulus, 50% Tensile Lap shear Elongation at break Clarity (% T at 500 nm)

(kNm-l ) (kNm-l ) (MPa) (MPa) (MPa) (%)

18 20 23 5.1 4.4 5.3 5.8 1.3 1.0 1.3 1.5 0.30 0.30 0.34 0.36 1.4 1.4 1.5 1.7 1.0 0.7 1.5 1.2 460 430 390 440
57 48 68 48

20

Order of addition

The effects of changes in the proportions and order of addition of the silica are shown in table 2. No significant differences were found in the cured rubber properties. All of the compounds gave good slump resistant properties. Increasing the proportion of silica added after the crosslinker did appear to improve the potential slump resistance of the formulations, as shown by their higher yield stress values. All subsequent formulations were compounded adding all of the filler after the crosslinker had been added, as used in formulation 5.
Silica moisture level

the lower bulk density materials. This was reflected in their lower yield stress value, viscosity (at 1 rpm) and STI values and higher penetration and extrusion rate results. On curing they also showed slightly lower physical properties. Based on these results all subsequent silicas were evaluated in their normal undensed form to avoid any dispersion problems.
Silica surface area

The effect of adsorbed moisture on the surface of fumed silica is a prime concern to RTV- 1 compounders. Normally, values of <1.0 wt. % or even <0.5 wt. % are desired. Higher moisture levels are believed to cause graininess (silicone gels) and lead to poor shelf life of the sealant. The results in table 3 show that gels were observed during compounding in the formulation using fumed silica with 3.0 wt. % adsorbed moisture. All of the remaining formulations had very similar initial theological and cured physical properties. A preliminary attempt was made to study the shelf stability of these sealants by aging them for two months at room temperature, followed by 7 days aging at 50C. This is believed to be equivalent to a total of 4 months aging at room temperature. The aged sealant samples showed a general increase in yield stress values and a slight decrease in viscosity. None of the sealants showed any evidence of curing in the tube during this rather short aging period. More extensive aging studies are planned.
Silica bulk density

Fumed silicas can be manufactured with a range of surface areas from 50 to 400 m2/g. It was anticipated that increasing the specific surface area of the filler would result in compounds with improved theological, cured physical and clarity properties. This would be countered by slower incorporation rates and more difficult dispersion properties. The results in table 5 examined a series of hydrophilic fumed silicas with surface areas ranging from 57 to 402 m2/g. No significant differences in silica incorporation times were observed, although the silicas were increasingly more difficult to disperse as the surface area increased above 200 m2/g. None of the formulations slumped but there was an improvement in theological properties as shown by higher yield stress values, 1 rpm viscosity, STI
Table 5 effect of fumed silica surface area
Formulation 2 (m /g) Surface area Processing and theological properties incorporation time (min) Dispersion level (mm) Skin time Yield value (Pa) (Pa s) Viscosity, 1 rpm STI Slump value (cm) (1.0mm) Penetration value Extrusion rate, 0.28 MPa (g/min) Cured physical properties 1 57 4 164 5 192 8 402

16 20 10 19 excellent very good good 26 14 24 24 300 700 530 700 32.6 68.7 90.6 81. 6 1.2 2.1 2.5 2.8 0 0 0 0 v.high 140 1 2 0 110 290 70 100 80

Increasing the bulk density of the fumed silica from 40-50 g/1 to ~85 g/1 by mechanical compaction caused dispersion problems as shown by the data in table 4. The densed silicas, in formulations 2 and 4, incorporated faster but caused incomplete dispersion of the silica as reflected by the poor and grainy appearance of the uncured sealants and lower transparency of the cured compounds. Although neither formulations 2 or 4 slumped under our

Shore A durometer Die B tear Peel adhesion Modulus, 50% Tensile

Lap shear Elongation at break Clarity (% T at 500 nm)

(kNm -l) (kNm -1 ) (MPa) (MPa)

(MPa) (%)

17 3.9 1.0 0.26

1.1 2.9 400 24

21 5.4 1.1* 0.34

1.6 0.8 430 63

23 5.8 1.5 0.36

17 1.2 440 68

23 6.0 1. 6* 0.37
1.6 0.6 410 62

All samples showed cohesive failure except * where - 40% adhesive failure occurred

values and lower penetration rate values, as the silica surface area increased from 57 to 192 m2/g. The extrusion rates of the sealants were strongly dependent on the silica surface area for materials with surface areas less than 200 m2/g as shown by the data in figure 1. Above this value all of the silicas imparted generally similar extrusion properties to the formulation. The cured physical properties of the formulations also showed a slight increase as the silica surface area increased from 57 to 192 m 2/g. The peel adhesion values shown in figure 2 generally increased steadily with increasing silica surface area. The sealants normally showed cohesive failure with the exception of formulations 4 and 8 which showed -4070 adhesive failure. As expected, clarity of the cured compounds increased with increasing surface area (smaller silica particle size). However, this trend was most obvious for silicas with surface area values below 192 m2/g. Above this value the clarity did not change significantly with increasing surface area. This result was initially unexpected, as prior work in hot air vulcanized silicone rubber showed 10 further increases in cured compound clarity as the fumed sili2 ca surface area increased from -200 to 400 m /g. This difference can probably be attributed to the incomplete dispersion of the smaller silica aggregates in the lower viscosity polymer (18 Pas) used here, compared with the much higher viscosity gum (60,000 Pas) used in the prior study. The current results show that there appears to be very little improvement in rheology control, cured physicals (except peel adhesion) or clarity in using fumed silicas with surface areas greater than -200 m2/g in a simple silicone sealant formulation, using the current moderate shear mixing equipment. It is interesting to note that over the past five years there has been a general trend among silicone rubber sealant manufacturers to switch from using high surface area fumed silica of 200 to 250 m2/g to lower surface area fumed silicas of 90 to 160 m 2/g in their formulations.
Silica loading

136 m2/g silicas. The results showed the generally ex petted trends as the silica loading increased: These were longer incorporation times, higher yield, viscosity and STI values and lower penetration and extrusion rate values. The cured physical properties also improved as expected. The clarity of the sealants was similar, showing good dispersion at all filler levels. It is interesting to compare the differences in compounding, rheology and reinforcement properties imparted by the 108 m2/g and 136 m2/g 2 silicas (~25 % difference in surface areas). The 108 m /g silica gave much faster incorporation times, as shown in figure 3. As expected at equivalent loadings the 136 m2/g silica imparted superior rheology control giving less slumping, higher yield values as shown in figure 4 and higher viscosity and STI values. The lower surface area silica imparted significantly higher extrusion rates as shown in figure 5. The cured physical properties imparted by the two silicas were generally very similar, although as expected the 136 m2/g silica values were higher. A comparison of the Die B tear values is shown in figure 6. The clarity of the compounds containing the higher surface area silica was superior due to the smaller silica particle size. The main advantage of the 108 m2/g fumed silica is its significantly faster (~ 40%) incorporation rate into the polymer. This could have commercial utility, especially for compounders using high throughput twin screw extruders and planetary mixers. The lower process viscosity imparted by the 108 m2/g silica should also allow faster tube packaging rates. The faster extrusion rates of these formulations may be useful in automated high speed assembly line applications. A final advantage of the 108 m2/g silica is its reduced moisture adsorption from the atmosphere at any given relative humidity. Typical equilibrium moisture pick-up values for silica samples with surface areas of 108, 136 and 164 m 2/g are shown in figure 7.
Surface treatment

The changes in theological and cured physical properties of the sealants, as the silica filler loading was increased from 7 to 21 parts, were studied using the 108 m2/g and

An alternate method to reduce the moisture pick-up of fumed silica, besides lowering its specific surface area, is to pretreat the surface of the silica with an organosilicon compound. Figure 8 shows the chemical groups found on the surface of hydrophilic fumed silicas. The surface
4

chemistry of fumed and precipitated silicas is generally similar. The only major difference is that a surface hy droxyl group is attached to virtually every silicon atom on the precipitated silica surface. This imparts greater surface hydrophilicity compared to fumed silicas and explains their normally higher adsorbed moisture contents. In the fumed silica treatment process some of the surface silanol groups (Si-OH), on which water molecules
Figure 7 equilibrium moisture adsorption for various surface area grades of fumed silica at room temperature

normally absorb, are replaced by hydrophobic organosilicon groups (e.g., Si-O-Si(CH3)3). A -200 m2/g fumed silica was treated at various levels with an organosilicon fluid. The theological and reinforcement properties of these silicas are compared to an untreated silica of similar surface area in formulations 1 through 4 of table 6. In formulation 5, the fully treated silica was evaluated at a 50?I0 higher loading (21 parts). The results at 14 parts silica loading showed that the theological properties decreased with increasing treatment level as indicated by the lower yield stress values,

Table 6 effect of pretreatment level on fumed silica surface

2 3 1 4 5 Formulation 20 100 100 40 %Treatment level 0 (parts) Fumed silica <---------14--------> 21 Processing and theological properties 10 10 13 (min) 8 8 Incorporation time good Dispersion level <------poor> (min) 24 34 26 22 12 Skin time (Pa) 700 430 110 370 340 Yield value (Pa.s) 81.6 55.8 30.1 51.1 30.5 Viscosity, 1 rpm 2.5 1.5 1.0 1.3 1.3 STI (cm) 0 0 0 >5 0 Slump value 190 140 Penetration value (0.1 mm) 110 170 110 120 60 200 200 100 Extrusion rate O 28 MPa (g/min] Cured physical properties 23 20 16 23 Shore A durometer 21 -1 (kNm ) Die B tear 5.8 5.1 4.7 4.2 6.5 -1 (kNm ) 1.5 1.6 Peel adhesion 1.5 1.4 5.0 (M Pa) 0.36 0.36 0.33 Modulus, 50% 0.29 0.38 Tensile (MPa) 1.74 1.29 1.31 1.57 1.02 (M Pa) 1.2 0.6 2.6 2.8 2.9 Lap shear (% ) 440 350 330 350 320 Elongation at break 66 59 57 58 Clarity (% T at 500 nm) 61

Table 7 comparison of precipitated silicas with fumed silica

5 3 2 Formulation <--Precipitated--> Type of silicas 2 136 149 138 (m /g) Surface area 180 (g/1 ) 180 Pour density 80 <--14--> 28 Loading (parts) Processing and theological properties 4 7 (min) 7 Incorporation time v.poor poor v.poor Dispersion level 20 (rein) 21 20 Skin time 0 0 (Pa) 0 Yield value 49.4 (Pas) 24.9 37.4 Viscosity, 1 rpm 1.1 2.1 1.5 STI >>5 >>5 >>5 (cm) Slump value (0.1 mm) [180] [220] [150] Penetration value Too high to measure Extrusion rate 0.28 MPa (g/min) Cured physical properties 14 22 16 Shore A durometer -1 Die B tear (kNm ) 4.2 3.2 6.1 -1 0.7 Peel adhesion (kNm ) 1.1 04 0.33 (MPa) 0.24 0.21 Modulus, 50% 1 .34 0.58 1 .52 Tensile (MPa) (MPa) Lap shear 0.7 0.6 0.6 230 290 Elongation at break (%) 390 1 4 1 3 5 Clarity (% T at 500 nm) [ ] values measured after O 1 seconds 6 Fumed 108

40
14 11 excellent

26
410 45.0 1.5

0
[120] 250 20 4.4 1.1 0.29 1.63 1.9 450 47

This difference is most clearly seen in examining the electron micrographs of typical samples of the two silicas, as shown in figures 9 and 10. The fumed silica is produced in a very dilute high temperature silica aerosol, where molten silica particles can collide and fuse into open-branched-chain silica aggregates. As expected, these materials have very low bulk densities (-40 g/1 ) and high DBP oil absorption values (-5 m 1 /g). In contrast, the precipitated silicas are made in a concentrated silica aquasol by the acid hydrolysis of sodium silicate. In this case the small silica particles form dense grape-like cluster aggregates of much higher bulk density (80 to 190 g/1) and lower DBP oil absorption values (3 ml/g). The open-branched-chain fumed silica ag-

viscosity (at 1 rpm), STI values and higher penetration and extrusion rate values. The formulation containing the fully treated silica slumped badly. The cured physical properties of the formulations also decreased as the level of silica surface treatment increased. Similar results have been observed in heat cured silicone rubber compounds. The inferior theological and reinforcement properties imparted by the partially and fully treated silica are probably related to the weaker interaggregate interaction between neighboring silica aggregates and between the silica and silicone polymer. For untreated silicas these interactions are via strong hydrogen bonding between the surface silanol groups on adjacent silica aggregates. In the case of the treated silica materials the interaggregate interaction is via the relatively weak London dispersion forces of the organosilicon groups (basically methyl groups). The theological and cured physical properties of a sealant- containing a treated silica can be made to be a closer match to those of a sealant containing an untreated fumed silica filler by increasing the treated silica loading, as shown in formulation 5 of table 6. However, the additional cost of the treated filler makes this an unattractive approach.
Precipitated silicas

The final portion of this study involved the comparison of several commercially available precipitated silicas having surface areas of 130 to 160 m2/g, with a 108 m2/g surface area fumed silica. These results shown in table 7 indicate that at equal loadings, the precipitated silicas imparted virtually no rheology control and very poor reinforcement properties, compared to the fumed silica. Increasing the precipitated silicas loading to twice the normal fumed silica level significantly improved the cured physical properties but did not solve the very poor theological properties. The clarity of the precipitated silica formulations was also inferior to that of fumed silica, making them unsuitable as fillers for glazing sealants. The differences in theological and reinforcement properties imparted to the sealants by these two types of silica are related to differences in their aggregate morphologies. 6

gregates are much more effective at building an open three dimensional network of interacting aggregates in a fluid or polymer, than the compact precipitated silica aggregates. This type of open floe network of silica aggregates throughout the liquid or polymer, where interaggregate bonds can be rapidly broken and reformed with the imposition and removal of stress forces, is essential for making a sealant with no slump and high extrusion rate properties. In addition, the silica imparts reinforcement by interaction of the silicone polymer with the silica surface. Due to its very open-branched-chain silica aggregates, most of the surface area (N2 BET) of the fumed silica is available for polymer-filler interaction. In contrast, due to the tight grape-cluster like aggregates, much of the surface area (N2 BET) of a precipitated silica is unavailable for polymerfiller interaction and hence at equal loadings and surface areas, fumed silica is a more effective reinforcing agent than precipitated silica.
Rheology

Table 8 attempt to correlate slump and yield stress values of sealants

Filler Hydrophilic and partially treated fumed silica 108 m2/g hydrophilic fumed silica Fully surface treated fumed silica Precipitated silica Loading Slump Yield stress value (parts) (cm) (Pa) 14 7 14 14&28 0 >290 230

0.1
>5 >>5

110 0

Rheology is the science of the flow and deformation of materials. It is essential to understand the flow behavior of these sealants, not only for the processing operations, but also during their actual application. Shear stress is a measure of the force per unit area of pressure applied, and shear rate is a measure of the rate at which the sealant is deformed. Therefore, the viscosity is a measurement of the resistance of the sealant to deformation under applied stress, or simply defined, as the ratio of shear stress to shear rate at a given shear rate. The yield value is a critical stress value below which no flow occurs. As Lippe8 has pointed out, a sufficiently high yield stress value should
Figure 11 comparison of rheograms of silicone sealants containing fumed and precipitated silicas

2000

CL

-a

1500

1000

500

17.5

35

52.5

70

Shear rate (see-~ )

assure both adequate sag resistance, a viscosity-dependent phenomenon and adequate slump resistance, a yield stress dependent phenomenon. In the present studies several different theological properties of the sealants including yield stress value, viscosity and shear thinning index were measured, using a cone and plate viscometer. An attempt was made to relate these basic theological measurements with the more practical slump, penetration and extrusion rate measurements used by industry to characterize sealants. Figure 11 compares the shear stress versus shear strain rate properties of sealants containing 14 parts of a 108 m2/g fumed silica and 14 parts of a 149 m2/g precipitated silica, formulations 6 and 2 listed in table 7. The fumed silica sealant shows a very pronounced knee in the stressstrain curve at a very low shear rate ( ~3 sec -l). Above this point, the yield stress value, the sealant flows much more readily. In contrast, the precipitated silica sealant shows no yield stress value and a virtually linear stress-strain relationship. The fumed silica sealant had a high yield stress value of 410 Pa, no slump, moderate penetration value [120] and moderate extrusion rate of 250 g/rein at 0.28 MPa. In contrast, the precipitated silica has a yield stress value of O, very high slump >>5cm, higher penetration value [180] and extremely high extrusion rate at 0.28 MPa. The yield stress value of a sealant is believed to be a measure of the number and strength of the interaggregate interactions between the particles forming the silica network in the sealant. This network must be broken down by stress forces, before significant flow of the sealant can occur. These stress forces may be either mechanical, as in the case of the rotating cone and plate of the viscometer, or applied pressure during the extrusion process or gravitational forces in the case of slumping. Increasing the fumed silica concentration in a sealant increases the number of interacting aggregates within the silica network thus increasing the yield stress value as shown in figure 4. This also reduces the penetration value and the extrusion rate, and increases the viscosity of the system. The silica network can be weakened by reducing the strength of the interaction between the aggregates in the network. This is clearly shown by the data in table 6 for the fumed silica treated at different levels with an organosilicon compound. Here the surface silanol groups, which can form very strong interaggregate hydrogen bonds, are progressively replaced with organosilicon groups (e.g., Si-O-Si (CH3)3) which only allow very weak van der Waals type interactions between the aggregates. In this case the yield stress values, viscosity and STI values decrease as the treatment level increases and the extrusion rate values increase. Surprisingly, the penetra7

Table 9 overall analysis of effect of changing variables on RTV-1 properties

Property Incorp. rate Formulation Crosslinker level Order of addition (increasing SiO 2 later) Silica properties Moisture level Bulk density Surface area 2 Loading 136 m /g 2 108 m / g Treatment level Ppt SiO 2 vs. fumed SiO 2 + Ease of dispersion Yield value + Effect of increase of parameters Slump Extrusion resistance rate Peel adhesion Tensile Elong.

Durometer

Tear

Clarity

o o
+

+ 0

o o 0

0
+

+ o 0

+ 0 0

+ 0 0

o 0 0 o o + +

0 0 0

o
+

o o

+ + +

o + +

+
+

+ + +
O = No change

+ + +

+ + + o

0 o o o

+ 0 0 0

+ = Increase = Decrease

tion values did not show any well defined trend. Finally the silica network-can be weakened by changing the morphology of the silica from three dimensional open chained aggregates of a fumed silica to the compact grape-like cluster aggregates typical of precipitated silicas. In these studies this resulted in the yield stress values decreasing to zero, lowered viscosities, although not STIS, much higher slump values >>5 cm and higher penetration values. Previous studies have shown that the sag values of paint films can be related to their yield values. The results from the current study given in table 8 indicate that a relationship exists between the yield stress value and the slump values of RTV- 1 silicone sealants. A review of all of the theological data generated in this study showed that correlations exist between yield stress and extrusion rate. As the yield stress values of sealants increased their extrusion rates decreased. Also, as the yield stress values increased the penetration values decreased. Finally, the extrusion rate of the sealants increased as their penetration values increased. None of the above correlations were strong enough for the graphs to be presented here. The poor correlations may be due to the fact that the rheology of penetration and extrusion rate is complex and dependent on both the yield stress and viscosity properties of the sealant. In contrast, the slump value of a sealant is primarily related to its yield stress value alone.
Summary

This article reviewed the properties of fumed silica which affect its performance as a rheology control and reinforcing filler for a simple silicone RTV- 1 sealant. Particular emphasis was placed on the use of a cone and plate viscometer to relate yield stress with slump, extrusion rate and penetration properties. Table 9 gives an overview of the effect of varying the silica properties on the sealant behavior. In general, precipitated silicas and surface treated fumed silicas impart inferior properties to the sealant. For the hydrophilic fumed silicas the important properties are bulk density, surface area, loading and moisture content. It was concluded that moisture levels of <1.0 wt. % do not affect sealant properties. Although only limited studies were made of the bulk density factor, it appears that adequate silica dispersion can be achieved with density values of <50 g/1. The optimum silica surface area appears to lie in the range of 100-150 m2/g. The lower surface area silica gives faster incorporation with slightly lower theological 8

and cured physical properties. The rheological measurements showed that slumping characteristics of the sealants were directly related to their yield stress values. The extremely high yield stress values could lower extrusion rates. Also, there was a general increase of extrusion rate as the penetration value was increased. The theological properties of the sealants were found to be strongly related to the morphology of the filler aggregates and the strength of filler interaggregate interactions. Hence, low surface area hydrophilic fumed silica remains the filler of choice for silicone RTV- 1 sealants. *Baysilone is a registered trademark of Mobay Chemical Corporation, Pittsburgh, PA. Acknowledgments The authors wish to thank Messrs. Rudiger Laufhuette and Charles Sailor and Mrs. Marilois Connell for their work in helping to prepare this paper; Dr. John Funt for useful discussions on sealant rheology; and Mr. Peter Hagen, Perennator NA, for useful discussions on silicone sealants and the generation of the penetration data. Finally, our thanks to the Cabot Corporation for giving us permission to publish this paper. References 1 French Patent No. 1,188,495 (1959). 2 L.B. Bruner, U.S. Patent No. 3,077,465 (1963). 3 W. Noll, Chemistry and Technology of Silicones, Academic Press, 1968. 4 W. Lynch, Handbook of Silicone Rubber Fabrication, Van Nostrand Reinhold, 1978. 5 J.M. Klosowski and G.A.L. Gant, ACS Symposium Series 113, 1979. M.D. Beers, ACS Rubber Division Meeting, Paper 9, June, 1981. J. V. Lindyberg, Elastomeric 114, 1 (1982). R.J. Lippe, Plastics and Rubber Processing, 51-54, June, 1980. 9 S. Brunauer, P.J. Emmett and E. Teller, J. Amer. Chem. SOC. 60, 309, (1938). 10 H. Cochrane unpublished work. 11 B.B. Boonstra, H. Cochrane and E.M. Dannenberg, Rubber Chem. Technol. 48, 4 (1975). 12 D. G. Miller, W. F. Moll and V. W. Taylor, Modern Paint and Coatings, 73, 4 (1983).
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