SilcoTek Corporation Gary Barone Using Chemical Vapor Deposition Processes to Enhance the Corrosion Performance of Steel Substrates SilcoTek Corporation Gary Barone

Topics About Us Products and Applications Product Performance Conclusion/Future Product Development

Semiconductor/Research MARKET AREAS APPLICATION AREAS SilcoNert™: Inertness Silcolloy™:Anti-Corrosion SilcoKlean™: Anti-Coking SilcoGuard™: Ultra-High Vacuum Analytical Pharmaceutical Environmental Petrochemical Chemical Process Semiconductor/Research SilcoNert 1000 (original inert coating) SilcoNert 2000 (most advanced inert coating) available through Swagelok. SilcoNert 2000 is used in sampling, instrumentation, gas chromatography consumables, process monitoring, emissions monitoring, oil and gas production/distribution and refining. Silcolloy (corrosion resistant coating) used in acidic corrosion environments. Recommended for chloride corrosion applications such at marine/salt corrosion, HCl exposure. SilcoGuard (low out gassing, ultra high vacuum coating) developed for high vacuum environments where high pumping speed is needed for improved productivity. UHV coating will allow up to 14x faster pump down. SilcoKlean (anti coking coating) developed to prevent catalytic coking in high temperature fuels and lubrication environments. SilcoKlean will reduce carbon build-up by 8x. Automotive

Basic Manufacturing Process Receive items Document – digital, customer contact Clean Standard: caustic ultrasonic bath, 2 systems Custom: solvation via other means Chemical Vapor Deposition (CVD) Process Vacuum 400ºC silicon-based deposition Pack, ship Parts are received and inspected. Customer is notified of part receipt. Parts are cleaned in an ultrasonic bath and queued for treatment. Batch CVD process ovens heat parts under vacuum. Semiconductor gas fills the oven chamber coating the parts. All surfaces exposed to the process gas will be coated. SilcoTek cannot mask select areas of a part due to the high process temperatures. After coating, parts are cleaned, inspected, packaged and shipped. The customer is contacted regarding order status and shipping.

Product Characterization Amorphous silicon CVD coating Density: 2.33 g/cm3 Melting point: 1410oC Max operating temp. 600oC to 1000oC: Silcolloy; SilcoNert 1000; SilcoGuard 450oC SilcoNert 2000 1200A to 5um thickness, minimal smoothing of surface

Coating Cross Section 316 SS Cross section of substrate/coating shows minor variations in coating thickness. Coating at this magnification appears to show a surface coating. But Auger depth profile shows layer diffuses into the substrate.

Auger Depth Profile Auger shows a 1200A silicon layer depth (red). Iron (green) shows the start of the substrate layer at 35min. Subsequent Auger and GD-OES data show iron/silicon interface can be up to several hundred angstroms thick. Providing a layer which is diffused (or meshed) into the surface, similar to Velcro. This diffusion creates a durable, flexible layer that will not delaminate.

Coating Capabilities: Substrates Tubing: 0.004” to 0.5” ID 2000+ ft. continuous lengths Complex geometry parts (inside and out) Fittings, valves, frits Block manifolds, sample vessels custom parts Restek is able to coat continuous lengths of tubing of +2000 feet. Custom components of complex geometry can be coated. Fittings, valves, frits can also be coated.

Sizes of reaction chambers “Standard” vessels: 12” diameter cylinder w/ 56” height 6” diameter cylinder w/ 72” height 10” diameter cylinder w/ 18” height 21” diameter cylinder w/ 42” height Large processing oven: 27” diameter x 26” deep Walk-in Oven: 4 feet by 4 feet by 5 feet 6 feet by 4 feet by 5 feet SilcoTek processes orders in a variety of reactors depending on part geometry and volume.

Substrates Which Coat Well 300 and 400 grade stainless steel High carbon steel Titanium Ceramics Borosilicate glass Inconel® Hastelloy® SilcoTek coats most common steel alloys, along with borosilicate glass.

Substrates with Issues Nickel / Nickel plating Aluminum* Monel® Copper Brass Gold and Silver plated components Chrome Plated components Magnesium Elastomers *heat-dependent Pure nickel and copper cannot be coated. Copper alloys cannot be coated but Nickel alloys can be coated. Most aluminum alloys will soften when exposed to our process temperatures and are not recommended. Some applications using 6061 aluminum may be coated. Elastomers cannot be coated due to high process temperatures.

Corrosion Resistance of Coatings

Silcolloy™ Corrosion Resistance: Stainless steel surfaces susceptible to attack from in chlorinated environments and acidic exhaust environments. Corrosion resistant deposition is insoluble in hydrochloric acid and unaffected in salt water environments. Silcolloy 1000 is a multi layer amorphous silicon coating designed to improve the corrosion resistance of steel or steel alloys. Silcolloy protects steel and stainless steel from chloride attack & is used in process, analytical and marine environments. Silcolloy is capable of withstanding temperatures up to 1000C making the coating an attractive option for customers looking for corrosion protection in high temperature environments. Silcolloy is a cost effective way to extend the life of steel, stainless steel or exotic alloys; but is not intended to be an alloy substitute. Because base metal attack can occur if the Silcolloy layer is compromised

Corrosion Resist studies External Evaluation Certified corrosion engineers (Matco) Spectroscopic analysis Mechanical testing Electrochemical Cyclic Polarization in neutral, acidic, alkaline Atmospheric corrosion ASTM moisture condensation Salt spray ASTM B117 Stress corrosion cracking (MgCl2; ASTM G36) SilcoTek partners with independent test laboratories to evaluate coating performance. Certified corrosion engineers, Matco Associates studied the corrosion performance of Silcolloy

ASTM G48 B Data: Pitting and Crevice Corrosion ASTM G48 method B; Pitting and Crevice Corrosion 6% Ferric Chloride solution 72hrs, 20ºC 316L Stainless samples w/Gasket wrap Sample Initial Weight (g) Final Weight Loss (g) Weight Loss (g/m2) Silcolloy™ Sample 17 10.4105 10.3710 0.0395 19 Silcolloy™ Sample 28 10.1256 10.0743 0.0513 25 Silcolloy™ Sample 47 10.1263 10.0742 0.0521 Bare Sample 27 10.0444 9.5655 0.4789 231 Bare Sample 34 10.1265 9.6923 0.4342 209 Bare Sample 37 10.1007 9.6276 0.4731 228 Pitting and Crevice Corrosion tests show an order of magnitude reduction in corrosion weight loss when comparing 316L coated stainless steel coupons with uncoated coupons.

ASTM G48 B (cont.) Bare 316L Stainless Steel coupon showing severe crevice corrosion Uncoated coupon shows significant corrosion at gasket. Note deep pitting as well.

ASTM G48 B (cont.) Corrosion resistant treated sample showing no crevice corrosion and slight pitting corrosion Coated coupon shows only slight pitting and no gasket area damage.

ASTM G61 Data: Cyclic Polarization ASTM G-61; Cyclic Polarization Electrochemical Corrosion Testing Acid, neutral, basic aqueous solutions with varying Cl- ion concentrations (100, 3000, 5000ppm) EG&G VersaStat System, 23ºC 316L vs. Silcolloy™ on 316L & 304L -CR vs 316L Raw: 50x improvement Ec = corrosion potential Ic = current density at Ec Eb = pitting potential CR = corrosion rate Neutral solution; 3000ppm Cl- Sample Ec, mV Ic, uA/cm^2 Eb, mV CR, mpy 316 L -418 0.096 370 0.04 Silcolloy™ 316 L  -533 0.002 1460 0.0009 304 L -435 0.145 361 0.06 Electrochemical corrosion tests show a 50x improvement over 304 and 316ss coupons.

ASTM B117 Data: Salt Spray ASTM B 117 – “Practice for Operating Salt Spray (Fog) Apparatus.” 4000 hour exposure 100 degree Fahrenheit 3.5% by weight sodium chloride Reproduces exposure to marine environments. 4000 salt spray tests show some corrosion in uncoated coupon and no corrosion in coated coupon

ASTM B117 Data (cont.) Silcolloy™ treated samples showed no signs of bleeding, rusting, or pitting corrosion

ASTM B117 Data (cont.) The non-treated samples showed some light surface rusting, but no signs of pitting corrosion. Some corrosion found at perforation in uncoated coupon

ASTM D4585 Data: Condensing Humidity ASTM D 4585, “Practice for Testing the Water Resistance of Coatings Using Controlled Condensation.” 1000 hour study 100 degrees Fahrenheit Distilled water Reproduces exposure to atmospheric conditions 1000 hour humidity testing shows no adverse affects.

ASTM D4585 (cont.) Silcolloy™ treated samples showed no signs of bleeding, rusting, or pitting corrosion

Silcolloy™ Advantages Longer Life: Extend lifetimes of equipment exposed to corrosive environments and/or process streams Protection: Protection of high value equipment in corrosive environments Inert: Provide enhanced corrosion resistance to analytical equipment while maintaining inert sample pathway High Temperature: High temperature stability up to 1000c Silcolloy saves money by extending the life of process components. Customers may choose to Silcolloy coat stainless steel components and replace corroded components as needed over the life of the system rather than pay premium pricing for Hastelloy or other exotic alloys. Over the life of the system, a Silcolloy coated system will reduce costs by 60% when compared to a comparable Hastelloy system.

Silcolloy™ Applications Manufacturing/Chemical Process streams containing HCl Environmental Continuous Emissions Monitoring exposed to stack gases from coal fired plants and incinerators Automotive Equipment used in Automotive Exhaust testing and catalytic converter studies Diesel EGR & Turbo systems Marine Some preliminary evaluation of coating in marine environments (offshore platforms) The principal market application for Silcolloy is for hydrochloric acid or other chloride corrosives in manufacturing, chemical and petrochemical environments. High temperature, corrosive environments, such as stack monitoring systems, are also key application markets.

Conclusions/Future Continual process improvement and new product development for coatings: Improving the hardness of coatings Improved corrosion resistant coatings Hydrophobic surfaces for moisture sensitive applications Protection of high nickel alloys such as Hastelloy® and Inconel® Hydrogen embrittlement resistance.

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