A molding based on a monolithic organic aerogel

Abstract

A molding based on a monolithic organic aerogel has a density in the range from 60 to 300 kg/m.sup.3 and a thermal conductivity in the range from 12 to 17.8 mW/m*K. The molding based on a monolithic organic aerogel has more than 30 vol.-% of pores with a diameter of less than 150 nm, and more than 20 vol.-% of pores with a diameter of less than 27 nm, based on the total pore volume. A process can be used to prepare the molding by compression.

Claims

1-13. (canceled)

14: A molding based on a monolithic organic aerogel, having a density in the range from 60 to 300 kg/m.sup.3, and a thermal conductivity in the range from 12 to 17.8 MW/m*K, measured according to DIN EN 12667:2001-05 at 10° C. and 101,325 Pa, and wherein the molding comprises more than 30 vol.-% of pores with a diameter of less than 150 nm and more than 20 vol.-% of pores with a diameter of less than 27 nm, based on a total pore volume, and wherein the molding is in the form of a sheet with a thickness in the range from 100 μm to 10 mm.

15: The molding as defined in claim 14, which has a compression strength in the range from 600-700 kPa, determined according to DIN EN ISO 844:2014-11.

16: The molding as defined in claim 14, which has a flexural strength in the range from 1000-5000 KPa, determined according to DIN EN 12089:2013-06.

17: The molding as defined in claim 14, wherein the monolithic organic aerogel is a monolithic aerogel based on polyurethane (PU) and/or poly urea (PUR) with less than 80% of polyisocyanurate (PIR) structures.

18: The molding as defined in claim 14, which has a density in the range from 140 to 240 kg/m.sup.3.

19: A process for preparing the molding as defined in claim 14, the process comprising: compressing a molding based on an organic aerogel with a density in the range from 50 to 140 kg/m.sup.3, and with a compression factor in the range from 5 to 70 vol.-%.

20: The process according to claim 19, wherein the compression is performed in a hydraulic or pneumatic press.

21: The process as defined in claim 19, wherein the molding based on an organic aerogel is compressed in the form of a sheet unidirectional in the direction of the thickness of the sheet.

22: The process as defined in claim 19, wherein the compression is performed in a hydraulic or pneumatic press at a temperature of the molding between 10 and 80° C.

23: A process for preparing the molding as defined in claim 14, the process comprising: a) reacting a mixture (A) comprising at least one polyfunctional isocyanate (a1), at least one aromatic amine (a2), and at least a catalyst (a3), in the presence of a solvent (B), to form a gel, b) drying the gel obtained in a) under supercritical conditions, to obtain a dried gel, c) optionally, cutting the dried gel into sheets with a thickness in the range from 0.1 to 10 mm, and d) compressing the dried gel to a density in the range from 100 to 300 kg/m.sup.3.

24: A thermal insulation material, comprising the molding according to claim 14 as an aerogel layer A), and at least one cover layer C) with a thickness in the range from 10 μm to 1 mm.

25: A process for preparing a thermal insulation material according to claim 24, the process comprising: a) reacting a mixture (A) comprising at least one polyfunctional isocyanate (a1), at least one aromatic amine a2), and at least a catalyst (a3), in the presence of a solvent (B), to form a gel, b) drying the gel obtained in a) under supercritical conditions, to form a monolithic aerogel, c) optionally, cutting the monolithic aerogel into sheets with a thickness in the range from 0.1 to 10 mm, d) compressing the monolithic aerogel from b) to a density in the range from 100 to 300 kg/m.sup.3, to obtain the aerogel layer A), and e) applying at least one cover layer C), optionally, by an adhesive layer B), to the aerogel aye A) obtained in d).

26: The thermal insulation material as defined in claim 24, wherein the thermal insulation material is a thermal insulation material in building and/or construction, in a refrigeration appliance, in an electronic device, in aerospace, and/or in a battery.

Description

EXAMPLES

[0098] Methods:

[0099] The thermal conductivity was measured according to DIN EN 12667:2001-05 with a heat flow meter from Hesto (Lambda Control A50) at 10° C. In the case of laminated and non-laminated sheets of 1-2 mm thickness, stacks of up to 9 sheets (15 cm*15 cm) were measured.

[0100] The compressive strength was determined according to DIN EN ISO 844:2014-11 with 6% strain.

[0101] Flexural strength was determined with three-point bending test according to DIN EN 12089:2013-06. Holding points were spaced 50 mm apart. Maximum bending radius was 90°. Sample dimension was ca. 100×20 mm. Samples laminated on one side were pressed on laminated side.

[0102] Friability was determined with a tumbling friability test according to ASTM C 421-77 with samples of 25×25 mm length and width and a thickness as reported in Table 4.

[0103] Pore volume was measured according to DIN 66134:1998-02 using a Nova 4000e pore size analyzer from Quantachrome Instruments. Approximately 15-20 mg of the samples were broken off from the original sample and placed in a measuring glass cell. The samples were degassed under 50 mm Hg vacuum and 60° C. for 15 h to remove any adsorbed components on the sample. The samples were weighed again prior to the surface area and pore size analysis.

[0104] Surface area measurements: Specific surface area was determined by Brunauer-Emmet-Teller (BET) method using low-temperature nitrogen adsorption analysis (at the boiling point of nitrogen, 77K) between the IUPAC recommended P/P0 range (0.05-0.30). The 1/((w.Math.(P0/P−1))) vs P/P0 graph yielded linear plot with correlation coefficients (r) above 0.999.

[0105] Pore size distribution: A low temperature nitrogen adsorption-desorption curve was determined in the P/P0 range (0.05-0.99). The pore size distribution was determined using the Barret-Joyner-Halenda (BJH method) which using the Kelvin model of pore filling for a given pore size. The theoretical maximum pore diameter measurable by this method is 190 nm.

[0106] Pore volume (occupied by pores less than 190 nm): The total mesopore volume was determined from the total volume (vads) of nitrogen adsorbed (at S.T.P conditions) on the pores at P/P0=0.99 and subsequently multiplying this value with a conversion factor that provides the value of liquid nitrogen filled inside the pores.

[0107] The total pore volume of the monolithic organic aerogel samples was calculated as difference of the specific volume of the sample and the specific volume of the solid polymer (skeletal volume). The specific volume of the solid polymer may be determined by pycnometry according to ISO 12154:2014-04. In the examples the specific volume of the isocyanate-based polymer was 0.65 cm.sup.3/g.

[0108] Materials: [0109] M200 oligomeric MDI (Lupranat M200) having an NCO content of 30.9 g per 100 g accordance with ASTM D-5155-96 A, a functionality in the region of three and a viscosity of 2100 mPa.Math.s at 25° C. in accordance with DIN 53018. [0110] MDEA 3,3′,5,5′-Tetraethyl-4,4′-diaminodiphenylmethane [0111] MEK Methylethylketone [0112] Ksorbate Potassium sorbate dissolved in monoethylene glycol (5%) solution [0113] TBA citrate Tetrabutyl ammonium citrate (25 wt.-% in MEG) [0114] Exolit OP560 Phosphorous polyol

[0115] Transparent Tape (CB1):

[0116] Ca. 0.06 mm thick transparent PP tape (width 5 cm) with contact adhesive (Enviropack® e-Tape)

[0117] Textile-Reinforced Tape (CB2):

[0118] Ca. 0.3 mm thick polymer tape (width 5 cm) with textile reinforcement and contact adhesive (Tesa® 4651 white)

[0119] Paper (CB3):

[0120] Office paper 80 g/m2 with a manually applied layer of glue-stick adhesive (Pritt® original glue stick)

[0121] Graphite Foil (CFB4):

[0122] Ca. 25 μm thick graphite foil with 10 μm electrically isolating polymer layer and contact adhesive (heat-spreader foil from ProGraphite)

[0123] Aluminum-Coated Paper (CFB5):

[0124] Ca. 0.3 mm thick aluminum-coated paper with contact adhesive

[0125] Mineral Fleece (CFB6):

[0126] Ca. 0.6 mm thick, fire-resistant mineral fleece (Innobra MIV 520 P) with a manually applied layer of glue-stick adhesive (Pritt® original glue stick)

Example 1

[0127] In a polypropylene container, 48 g M200 were stirred in 220 g MEK at 20° C. leading to a clear solution. Similarly, 8 g MDEA, 2 g Ksorbate solution (5% in MEG), 2 g Exolit OP560 and 4 g Butanol were dissolved in 220 g MEK to obtain a second solution. The solutions were combined in a rectangular container (20×20 cm×5 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO2 in a 25 l autoclave leading to a porous material.

[0128] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min (Examples 1-1, 1-2).

[0129] A wrench was placed on top of the porous plate of example 1-C and compressed. The wrench was afterwards embossed with its logo on the surface of the plate.

Example 2

[0130] In a polypropylene container, 25.6 g M200 were stirred in 146.67 g MEK at 20° C. leading to a clear solution. Similarly, 5.33 g MDEA, 1.33 g Ksorbate solution (5% in MEG), 1.33 g Exolit OP560 and 2.67 g Butanol were dissolved in 146.67 g MEK to obtain a second solution. The solutions were combined in a rectangular container (16×16 cm×3 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO2 in a 25 l autoclave leading to a porous material.

[0131] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min (Examples 2-1, 2-2, 2-3, 2-4).

Example 3-C

[0132] In a polypropylene container, 22.4 g M200 were stirred in 121.6 g MEK at 20° C. leading to a clear solution. Similarly, 5.33 g MDEA, 1.33 g Ksorbate solution (5% in MEG), 1.33 g Exolit OP560 and 2.67 g Butanol were dissolved in 121.6 g MEK to obtain a second solution. The solutions were combined in a rectangular container (16×16 cm×3 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO.sub.2 in a 25 l autoclave leading to a porous material.

Example 4-C

[0133] In a polypropylene container, 22.4 g M200 were stirred in 96.8 g MEK at 20° C. leading to a clear solution. Similarly, 5.33 g MDEA, 1.33 g Ksorbate solution (5% in MEG), 1.33 g Exolit OP560 and 2.67 g Butanol were dissolved in 96.8 g MEK to obtain a second solution. The solutions were combined in a rectangular container (16×16 cm×3 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO2 in a 25 l autoclave leading to a porous material.

Example 5-C

[0134] In a polypropylene container, 22.4 g M200 were stirred in 54.3 g MEK at 20° C. leading to a clear solution. Similarly, 5.33 g MDEA, 1.33 g Ksorbate solution (5% in MEG), 1.33 g Exolit OP560 and 2.67 g Butanol were dissolved in 54.3 g MEK to obtain a second solution. The solutions were combined in a rectangular container (16×16 cm×3 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO.sub.2 in a 25 l autoclave leading to a porous material.

[0135] The results are summarized in table 1. The compressed porous plates show a significant lower thermal conductivity and a higher flexural strength at higher density.

Example 6

[0136] Preparation of Compressed Monolithic Aerogel Layer A1:

[0137] In a polypropylene container, 48 g M200 were stirred in 220 g MEK at 20° C. leading to a clear solution. Similarly, 6 g MDEA, 2 g Ksorbate solution, 2 g Exolit OP560 and 6 g Butanol were dissolved in 220 g MEK to obtain a second solution. The solutions were combined in a rectangular container (20 cm×20 cm×5 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO.sub.2 in a 25 l autoclave leading to a porous material.

[0138] A slab of the porous material of 15×15×1.5 cm was cut to sheets of 15×15 cm and 1-3 mm thickness using a band saw.

[0139] Preparation of Compressed Monolithic Aerogel Layer A2:

[0140] Porous plates obtained as described above for the monolithic aerogel layer A1 were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 20-25 cm/min. In Table 1 the thickness reduction is listed as compression in %.

Examples 6-1 to 6-11

[0141] Pre-cut strips of adhesive tape (CB1), textile tape (CB2), paper with a layer of glue-stick adhesive (CB3), graphite foil (CFB4), aluminum coated paper (CFB5) or mineral fleece with a layer of glue-stick adhesive (CFB6) were pressed manually with the adhesive layer onto a sheet of monolithic aerogel layer A1 and A2. In the case of CB1 and CB2, for samples of 5 cm width or less, one layer of tape was used per side. In case of samples with more than 5 cm width, tape layers were applied in such a way as to cause an overlap of ca. 5-10 mm between layers. The laminate structure, thickness and mechanical properties of the thermal insulation material are summarized in Table 1.

[0142] Examples 6-3 to 6-7, 6-8, 6-10 and 6-11 show no delamination in three-point-bending test, if bent with tape layer on outside no delamination occurs. Minimum diameter is the diameter without visible damage when bent or rolled. In case of sheets with lamination on one side the sheet was bent over the side without cover layer. Sheets are considered not reusable, if the material breaks and/or partial delamination occurs after bending to minimum rolling diameter.

[0143] The results are summarized in table 2.

Example 7

[0144] In a polypropylene container, 48 g M200 were stirred in 220 g MEK at 20° C. leading to a clear solution. Similarly, 8 g MDEA, 2 g Ksorbate solution (5% in MEG), 2 g Exolit OP560 and 4 g 1-butanol were dissolved in 220 g MEK to obtain a second solution. The solutions were combined in a rectangular container (20×20 cm×5 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO2 in a 25 l autoclave leading to a porous material.

[0145] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min (Examples 7-C to 7.4). The results are summarized in table 3.

Example 8

[0146] In a polypropylene container, 25.6 g M200 were stirred in 220 g MEK at 20° C. leading to a clear solution. Similarly, 5.44 g MDEA, 0.67 g TBA-Citrat solution (25% in MEG), 1 g Exolit OP560 and 2.67 g 1-butanol were dissolved in 220 g MEK to obtain a second solution. The solutions were combined in a rectangular container (20×20 cm×5 cm height) by pouring one solution into the other, which led to a homogeneous mixture of low viscosity. The container was closed with a lid and the mixture was gelled at room temperature for 24 h. The resulting monolithic gel slab was dried through solvent extraction with scCO2 in a 25 l autoclave leading to a porous material.

[0147] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min (Examples 8-C to 8.4). The results are summarized in table 3.

Examples 9-12

[0148] Example 9 was repeated with different amounts and concentrations of raw materials as shown in Table 5 to obtain monolithic aerogel samples with different densities and thickness.

[0149] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min to obtain compressed plates with thickness about 8 mm. The results are summarized in table 4.

[0150] Example 11-4 shows a mass loss of 0.3 wt.-% in the friability test, which is much lower than the mass loss of 1.7 wt.-% for comparative Example 10-C.

Examples 13 and 14

[0151] All steps were carried out at 20° C. Examples 13 (1 wt.-% alginate) and 14 (2 wt.-% alginate) were prepared by adding 28 g (13) or 56 g (14) sodium alginate to 2500 g water in a beaker and stirring overnight with a laboratory stirrer. Afterwards, 8.2 g (13) or 16.3 g (14) calcium carbonate powder were dispersed in water using a rotor-stator mixer, and the obtained dispersion was immediately added to the alginate solution while stirring. 6.8 g (13) or 13.6 g (14) D-glucono-δ-lactone (GDL) were dissolved in 66.7 g water by stirring intensely for 10 s, and the resulting solution was then added to 750 g of the alginate/calcium carbonate mixture followed by stirring of the resulting mixture for 30 s. The mixture was immediately poured into polymer molds of 20×20 cm to a height of 10-15 mm, and the filled molds were left for gelation of the mixture overnight. The liquid expelled from the gel during gelation was removed every 2-6 h. The obtained gel slabs were aged in 750 g of a previously prepared calcium chloride solution (15 g calcium chloride in 2975 g water) for 24 h. The gel liquid was exchanged from aqueous solution to ethanol by placing the gel slab for 24 h each in 750 g of 20 vol.-%, 40 vol.-%, 60 vol.-%, 80 vol.-% ethanol in water and finally pure ethanol for 24 h. The gel slabs were dried using supercritical carbon dioxide to obtain alginate porous plates.

[0152] The obtained porous plates were compressed for 2 seconds using a hydraulic press (Schmidt Maschinentechnik) with press plates (30×30 cm) at 25° C. with a pressure in the range of 30-60 kN/900 cm.sup.2 and a press speed of 22.8 cm/min to obtain compressed plates with thickness about 8 mm. The results are summarized in table 4.

TABLE-US-00001 TABLE 1 Physical and mechanical properties of Examples 1 to 5 Thermal Compression conductivity [% of [mW/m * K] Compressive Flexural original Thickness Density (p = 1 bar, strength strength Bending Pressure Example thickness] [mm] [kg/m.sup.3] T = 10° C.) [kPa] [kPa] [mm] [kN] 1-C 0 13.1 125 18.5 506 700 7.8 1-1 28 9.4 181 16.9 613 1280 12 1-2 42 7.6 237 17.0 668 2470 18.6 2-C 0 14.9 97 19.0 2-1 15 12.6 114 17.5 30 2-2 32 10.1 143 16.2 31 2-3 51 7.3 198 15.9 36 2-4 62 5.6 258 17.6 4370 10.1 58 3-C 0 12.3 108 18.7 680 4.9 4-C 0 10 130 18.5 1250 6.6 5-C 0 6.2 216 22.2 4240 9.8

TABLE-US-00002 TABLE 2 Properties of laminated sheets of Example 6 Bending Bending Reusable Bending strength strength Min. after Layer A Thickness Max. at max. at at Bending diameter bending Com- laminated Thermal bending bending 10 mm 20 mm to 90° when to min. Laminate pressed sheet ca. conductivity strength strength bending bending without Delam- bent/rolled rolling Example structure by [mm] [mW/m * K] [kPa] [mm] [kPa] [kPa] breaking ination [mm] diameter 6C-1  A1  0% 0.9 19.4 — — — — — — Breaks at 50 No 6C-2  A2 33% 1.0 16.7 2300 11 3200 Breaks No — Breaks at 50 No 6-1 CB1/A1  0% 0.9 20.3 — — — — — — — — 6-2 CB1/A1/CB1  0% 1.0 21.0 — — — — — — — — 6-3 CB1/A2 33% 1.1 17.8 3300 11 3200 Breaks No No 10 No 6-4 CB1/A2/CB1 33% 1.2 18.2 5300 11 5300 3900 Yes No 10 Yes 6-5 CB2/A2 33% 1.3 — 2600 9 2800 Breaks No No  5 No 6-6 CB2/A2/CB2 33% 1.6 — 5500 13 5300 4700 Yes No  5 Yes 6-7 CB3/A2/CB3 33% 1.3 — 11500  9 8100 6800 Yes Very 10 No little 6-8 CFB4/A2/CFB4 33% 1.0 19.0 — — — — — No — — 6-9 CFB5/A2/CFB5 33% 1.6 — — — — — — Some — —  6-10 CFB4/A2/CFB4 33% 2.0 18.0 — — — — — No — —  6-11 CFB6/A2/CFB6 33% 2.2 — — — — — — No — —

TABLE-US-00003 TABLE 3 Physical and mechanical properties of Examples 7 and 8 Thermal conductivity Total pore pore [mW/m * K] pore Volume Volume Compression Thickness Density (p = 1 bar, volume <150 nm <27 nm Example [Vol.-%] [mm] [kg/m.sup.3] T = 10° C.) [cm.sup.3/g] [cm.sup.3/g] [cm.sup.3/g] 7-C  0% 1.5 130 18.9 7.0 1.4 1.1 7-1 17% 1.3 150 17.5 6.0 2.4 1.3 7-2 33% 1.1 185 17.0 4.8 3.1 1.7 7-3 50% 0.8 246 17.1 3.4 2.2 2.0 7-4 67% 0.5 374 20.3 2.0 2.0 2.0 8-C  0% 1.4 101 17.4 9.2 4.5 1.6 8-1 17% 1.3 110 16.8 8.4 4.1 2.0 8-2 33% 1.0 139 15.7 6.5 3.4 2.6 8-3 50% 0.8 185 15.5 4.8 3.6 3.4 8-4 67% 0.5 279 19.7 2.9 2.5 2.5

TABLE-US-00004 TABLE 4 Physical and mechanical properties of Examples 9-14 Thermal conductivity Total pore pore Com- [mW/m * K] Flexural Bending pore Volume Volume pression Thickness Density (p = 1 bar, strength Bending modulus volume <150 nm <27 nm Example [Vol.-%] [mm] [kg/m.sup.3] T = 10° C.) [MPa] [mm] [MPa) [cm.sup.3/g] [cm.sup.3/g] [cm.sup.3/g  9-C 0 7.9 96 18.2 0.6 9.3 18 9.8  9-1 29 8.0 94 16.9 0.4 5.5 11 10.0 10-C 0 7.7 130 18.3 1.1 10.2 33 7.0 10-1 21 7.9 129 16.3 0.9 11.3 26 7.1 10-2 45 8.0 123 15.5 0.6 8.8 15 7.5 11-C 0 7.9 153 19.0 1.9 7.3 84 5.9 11-1 10 7.8 150 17.4 1.1 9.2 36 6.0 11-2 30 8.1 141 15.7 1.0 11.1 27 6.4 11-3 18 7.9 182 17.7 1.8 11.9 56 4.8 11-4 26 8.1 175 16.5 1.6 11.9 47 5.1 11-5 45 7.9 183 15.2 1.4 10.8 41 4.8 12-C 0 7.7 224 23.2 2.6 9.5 101 3.8 12-1 29 8.1 214 17.7 2.3 12.4 65 4.0 12-2 38 8.1 212 16.7 2.2 12.4 60 4.1 12-3 18 8.0 270 22.5 2.1 5.3 123 3.1 12-4 46 7.9 275 18.7 2.5 7.8 102 3.0 13-C 0 14.3 19.4 13-1 19 11.6 17.4 13-2 35 9.3 16.1 14-C 0 15.7 17.9 14-1 24 11.9 16.2 14-2 34 10.3 15.5

TABLE-US-00005 TABLE 5 Chemical composition of Examples 9-12 Exolit Ksorbate OP MDEA solution 560 Butanol M200 MEK Example [g] [g] [g] [g] [g] [g]  9-C 2.31 0.58 0.58 1.16 13.86 156.00  9-1 2.32 0.58 0.58 1.16 13.95 231.81 10-C 3.00 0.75 0.75 1.50 18.02 150.73 10-1 3.03 0.76 0.76 1.52 18.19 204.74 10-2 3.03 0.76 0.76 1.52 18.19 302.36 11-C 3.47 0.87 0.87 1.73 20.79 147.22 11-1 3.49 0.87 0.87 1.75 20.95 175.23 11-2 3.47 0.87 0.86 1.73 20.79 233.99 11-3 4.33 1.08 1.08 2.17 25.99 184.03 11-4 4.32 1.08 1.08 2.16 25.91 216.68 11-5 4.33 1.08 1.08 2.17 25.99 292.49 12-C 5.08 1.27 1.27 2.54 30.49 134.94 12-1 5.11 1.28 1.27 2.56 30.67 217.15 12-2 5.07 1.27 1.26 2.53 30.41 254.36 12-3 6.48 1.62 1.62 3.24 38.88 172.05 12-4 6.50 1.62 1.62 3.25 38.99 276.04