High Performance Carbon Black Pigments. Reprinted with permission from Paint & Coatings Industry, October 2012

Transcription

1 High Performance Pigments Reprinted with permission from Paint & Coatings Industry, ctober 20

2 Carbon black pigments in modern coating systems With more than 100 years of experience, rion Engineered Carbons LLC is your source for pigment performance in solvent-borne, water-borne and solventless coating systems. Select from a complete family of gas black and furnace black pigments to achieve the balance of properties you need from jetness and tint strength, to dispersibility and stability. rion s HIBLACK, NERX, PANTHER, Special Black, Colour Black and PRINTEX carbon blacks are known the world over for their quality and consistency. ur Applied Technology Centers can help solve challenges for applications such as high-jetness automotive base coats, rapid-curing UV industrial coatings, eco-friendly architectural paints, and conductive formulations. For a copy of our new brochure featuring rion s carbon black pigments for coatings, contact us today. Focused, Innovative, Responsive. The Americas rion Engineered Carbons LLC 4501 Magnolia Cove Drive Suite 106 Kingwood, TX USA phone Americas-Pigments@orioncarbons.com Europe / Middle East / Africa rion Engineered Carbons GmbH Hahnstrasse Frankfurt am Main Germany phone EMEA-Pigments@orioncarbons.com Asia / Pacific rion Engineered Carbons Trading (Shanghai) Co., Ltd. Room , BM InterContinental Business Center 100 Yutong Road, Shanghai P. R. China phone APAC-Pigments@orioncarbons.com

3 High-Performance Pigment Advances Meet Emerging Needs Performance requirements for carbon black pigments are increasingly important in the development of advanced coating, ink and polymer formulations as the need for more eco-friendly products grows. The overall greening trend of the global coatings industry has several implications for pigment blacks. Coatings manufacturers are demanding raw materials that are less toxic and more compliant with existing (and future) environmental regulations. At the same time, carbon black pigments, in many cases, must deliver outstanding coloristic performance in both waterborne as well as solventborne systems. New highperformance pigments can help meet these emerging needs through the following new developments. Improved Waterborne Performance: Thanks to a technical modification of the furnace black reactor, it is possible to manufacture a new class of fine-particle-size carbon black to meet the more demanding dispersion and performance needs in waterborne formulations. These unique properties provide high jetness and a distinct bluish undertone, while maintaining good stability in waterborne applications. Raw Material Reduction and Sustainability: The same technology used to provide high performance in waterborne applications can be further enhanced through surface modifications, and result in carbon black pigments that can give outstanding performance in both aqueous and solvent systems. The coatings industry is pushing suppliers for more sustainable raw materials, in part to be less dependent on fossil fuel feedstocks and related price volatility. Another driver is the move toward corporate sustainability. Although the move toward high-performance carbon black for waterborne coatings is a step in the right direction for eco-friendly formulations, it does not meet the need for sustainability. Therefore we developed a new grade of carbon black pigment using renewable feedstocks. This multi-functional carbon black allows formulators of coatings, inks and polymeric materials to develop truly sustainable products. FIGURE 1 Stabilization of carbon black in a waterborne system. Waterborne system: Solubilized binder electrostatic stabilization of the carbon black pigments Solubilized binder ionic or non-ionic additive binder with functional groups Waterborne system: Binder dispersion ionic or non-ionic additive emulsifier binder (in micelle) TABLE 1 Calculation of black value (M Y ), color-dependant black (M C ) and undertone (). Description Value Formula Black value (jetness) M Y 100 log(100/y) Black value including color M C 100 [log(xn/x) - log(zn/z) + log(yn/y)] Undertone (hue) 100 [log(xn/x) - log(zn/z)] By Thomas M. Papasso, Technical Market Manager rion Engineered Carbons LLC, Kingwood, TX

4 High-Performance Pigment Advances Meet Emerging Needs FIGURE 2 Evaluation of carbon black pigments in commercially available PUR basecoat/acrylic clearcoat. M Y Jetness (M Y ) Undertone () Black 1 Black 2 Black 3 Colour Black FW 171 FIGURE 3 Typical oxygen-containing groups on the surface of an aftertreated carbon black pigment. Phenol H Carboxyl H Lactone FIGURE 4 Color performance in 2K PU solvent-based coating system. M C H XPB 255 Colour Black FW Improved Resource Management: Carbon black is often considered the most difficult pigment to disperse, especially in waterborne systems. It typically requires the use of milling equipment, special additives and long periods of milling. ur new dry dispersion technology allows for easy dispersion of carbon black into an aqueous system with a dramatic decrease in time, energy consumption and the elimination of dispersing aids. To fully appreciate the impact of these developments, it is important to understand the general dispersion parameters and characteristics of carbon black pigments. Dispersion Considerations for Waterborne Systems Water is a highly polar solvent with high surface tension and insufficient wetting properties. Thus, for proper dispersion and stabilization of carbon black pigments in waterborne coatings, the use of wetting and dispersing additives is essential. The carbon black pigment and polymeric dispersion additive or binder must be compatible. Two ways exist to prepare waterborne coatings: A mill base consisting of: polymeric binder as an aqueous dispersion or solution (that is stable against temperature and shear forces), plus wetting agent, defoamer, amine and pigment. A mill base without binder consisting of: polymeric additives (instead of the binder), plus defoamer, amine and pigment. The advantage of this system is the high carbon black pigment concentration, improved coloristic properties and universal applicability. Proper adjustment of the binder ph in both systems is necessary to maximize coating performance. In waterborne coatings, electrostatic pigment stabilization is important. A mutual repulsion of pigment particles results from equally charged surfaces. To achieve this, the pigment surface is coated with ionic wetting and dispersing agents, or non-ionic agents with segments of different polarity. The choice of ionic or non-ionic additives depends on the properties of the pigment selected (Figure 1, p. 22). Furthermore, in waterborne dispersions, where the binder exists as polymer lattices (binder in micelle), there is almost no interaction between binder and pigment surface, so pigment dispersion must be assured by wetting and dispersing agents. In waterborne coatings, use of dispersing additives has always been essential, with concentration typically recommended in the range of mg per m 2 /g particle surface area. However, a recent advancement by rion in the area of dry carbon black pigment dispersions eliminates the need to use wetting additives and will be discussed. Calculating Jetness and Hue DIN , Determination of the Blackening Value of Pigment Blacks, provides a method for quantifying the degree of blackness or M Y value. The color-dependent black value M C differs from M Y by taking into account the precise undertone or hue of the black pigment. The hue value indicates the degree of brown or blue shade. It has been determined that the undertone of a black color also affects the visual assessment of jetness. A blue-shade

5 tint, for example, increases jetness, while a brown-shade tint decreases jetness. The higher the value for M Y and M C, the greater the perceived jetness or blackness. The higher the value the bluer the hue. A negative value indicates a brown shade. Table 1 (p. 22) shows the calculations to describe jetness and undertone. TABLE 2 Binder-free mill base formulation with CLUR BLACK FW 171. Raw Material Weight (g) Water Tego Dispers 760W, 35% Tego Foamex AMP Carbon black Wetting additive to carbon black 80% Carbon black pigment concentration 15.6% TABLE 3 Average ADF test results for CLUR BLACK FW 171 in PUR basecoat/acrylic clearcoat system. Panel (2K PUR Base/ FW 171 FW 171 Acrylic Clearcoat) Before ADF After ADF Delta (D) Gloss Gloss L* a* b* de* = 0.72 High-Performance for Waterborne Systems Technical modifications to the furnace black reactor resulted in a new class of carbon black pigment with very small mean particle size, narrow primary particle-size distribution and narrow aggregate-size distribution. The benefit of these unique properties is a carbon black pigment with high jetness, a distinct bluish undertone and very good stability in waterborne applications. To test the performance of CLUR BLACK FW 171, a typical binderfree mill base was prepared (Table 2). The performance of CLUR BLACK FW 171 was tested in a commercially available PUR basecoat/acrylic clearcoat system using the mill base in Table 2. The concentration of carbon black pigment in the final letdown was 1%. A study was conducted versus other commercially available high-color carbon black pigments (Figure 2, p. 23). The data shows that CLUR BLACK FW 171 outperforms the other pigments, providing higher jetness with a strong blue hue. High-color, high-performance carbon blacks like CLUR BLACK FW 171 are required to achieve superior exterior exposure performance and weathering. Although excellent UV performance is inherent with fine-particlesize carbon black pigments, coating manufactures continue to require two years of Florida weathering data. Unfortunately, weather conditions are unpredictable. The total UV exposure and precipitation in Florida can differ greatly from year to year and create unpredictable results with the same test sample. After exposure to environmental conditions, coated films can also show great differences in acid fastness, depending on whether their FIGURE 5 Masstone and tint results for XPB 255 vs. similar carbon black pigments. M Y XPB 255 Jetness (M Y ) Undertone () Colour Black FW 171 Colour Black FW 200 FIGURE 6 Masstone results in 2K polyurethane formulation. M Y Jetness (M Y ) Undertone () Printex Nature Printex 300 Printex 55 Printex 45 FIGURE 7 Relative tint strength and floating behavior results in the 2K polyurethane formulation. Relative Tint Strength (%) Relative Tint Strength (%) Floating Behavior (%) 80 Printex Nature Printex 300 Printex 55 Printex Floating Behavior (%)

6 High-Performance Pigment Advances Meet Emerging Needs FIGURE 8 Masstone results in a 2K alkyd/melamine formulation. M Y Jetness (M Y ) Undertone () Printex Nature Printex 300 Printex 55 Printex 45 FIGURE 9 Relative tint strength and floating behavior results in the alkyd/melamine formulation. Relative Tint Strength (%) Relative Tint Strength (%) Floating Behavior (%) 90 Printex Nature Printex 300 Printex 55 Printex 45 1 FIGURE 10 Masstone results in a 1K waterborne polyurethane formulation. M Y Jetness (M Y ) Undertone () Printex Nature Printex 300 Printex 55 Printex Floating Behavior (%) initial exposure was in a rainy period or from intense UV radiation (i.e., the primary difference between summer and winter in Florida). To better predict the performance of high-color carbon black pigments, rion utilizes the ADF (acid, dew and fog) weathering test. The ADF test consists of exposing paint specimens to different artificial weathering cycles in specially designed environmental test chambers. Weathering cycles were selected to best reproduce the harsh weather conditions in Florida. Different climatic conditions, such as UV radiation, heat and the application of distilled water or acid rain, alternate during the test. The ADF test is the first test method to satisfy the following requirements: The climatic changes in the test chambers, simulating weather conditions in Florida throughout the year, are tightly controlled for constant, reproducible test conditions; Combination of an acidic atmosphere with UV radiation; Appropriate analysis in order to simulate the precipitation in Florida; Strong correlation between results of the outdoor tests in Florida and the simulated weather conditions. Table 3 (p. 24) displays the CIE lab and gloss results after 42 days of ADF testing for CLUR BLACK FW 171 in a 2K PUR basecoat/acrylic clearcoat. for Waterborne and Solvent-Based Systems XPB 255 is an after-treated carbon black pigment. It is characterized by a very narrow distribution of mean primary particle size, as well as a narrow distribution of both primary particle and aggregate size. The after-treatment process generates a functional surface with oxygen-containing groups (Figure 3, p. 23). When incorporated into a coating system, these groups induce better wetting and dispersion properties. An enhanced interaction with polar binders significantly improves the stabilization of carbon black pigments. The volatile content or degree of oxidization is often used to characterize oxygen-containing surface groups. XPB 255 has a % volatile matter at 950 C. TABLE 4 2K polyurethane mill base and let down. Mill Base Formula Weight (g) Degalan VP 4157 (60%) Butyl acetate Carbon black 8.25 Letdown Formula CB Millbase from above Degalan VP 4157 (60%) Solvent reducer Desmodur N75 MPA (75%) 6.00 Total quantity of carbon black pigment 2%

7 The coloristic properties of XPB 255 were tested at a total carbon black pigment concentration of 2.2% in a solvent-based 2K PU coating system, based on an acrylic binder. Table 4 (p. 26) lists the formulation. Figure 4 (p. 23) displays the color performance of XPB 255 vs. CLUR BLACK FW 200, a popular high-performance carbon black typically utilized in automotive applications. XPB 255 shows a higher jetness (M Y = 302) with less bluish undertone ( = 5.6) compared with CLUR BLACK FW 200 (M Y = 289, = 11.5). The M C, which displays the overall visual impression of the final coating, discloses the significant improvement of XPB 255. The coloristic properties of XPB 255 were also tested in a waterborne 1K polyurethane system with a binder-free mill base. To improve the dispersion process, as is typical in waterborne systems, 70% wetting additive on carbon black pigment was used. Table 5 lists the complete formula. In the tested 1K polyurethane waterborne system (Figure 5, p. 24), XPB 255 displays higher jetness than CLUR BLACK FW 171 and CLUR BLACK FW 200. The bluish undertone is slightly less pronounced than that of CLUR BLACK FW 171, but XPB 255 is universally applicable across 1K PU waterborne systems. New Pigment from Renewable Feedstock rion Engineered Carbons developed PRINTEX Nature, a new carbon black pigment based on renewable feedstocks such as plant oils for use in coatings, printing inks and polymer formulations. If the new pigment is combined with natural-based binder systems and bio-solvents, it is possible to achieve more than 90% sustainable content in a formulation. Performance is similar to that of traditional carbon black pigments, with colloidal properties that make it ideal for medium jetness and tinting. It can also be used in indirect food contact, where low PAH (polycyclic aromatic hydrocarbon) is necessary. Testing shows PRINTEX Nature is well suited for a range of coating systems. Performance was evaluated in three types of formulations: 1) a solvent-based 2K polyurethane; 2) a standard alkyd/melamine baked enamel; and 3) a 1K waterborne. The renewable feedstock-based furnace black was compared to three other regular color furnace grades of carbon black with similar colloidal properties. Table 6 (p. 29) lists the 2K polyurethane test formulation. Tables 7 and 8 (p. 30) outline the masstone, tint, appearance and viscosity of the formulas. PRINTEX Nature displays similar appearance properties to standard carbon black pigments in terms of haze and gloss. The viscosity of the samples also shows similar characteristics. Figure 6 (p. 24) displays the masstone data of the test samples. PRINTEX Nature and PRINTEX 55 had similar jetness, but PRINTEX 300 and PRINTEX 45 provided greater jetness than PRINTEX Nature in this system. The test samples all displayed a similar brown undertone, with PRINTEX 300 being the least brown. Figure 7 (p. 24) displays relative tint performance. The test samples all displayed a similar tint performance; but PRINTEX Nature was the strongest and exhibited the best floating stability in a rub-up test. FIGURE 11 Relative tint strength and floating behavior results in the 1K waterborne polyurethane formulation. Relative Tint Strength (%) Relative Tint Strength (%) Floating Behavior (%) 80 Printex Nature Printex 300 Printex 55 Printex 45 1 FIGURE Coloristic results of waterborne coatings based on XPB 430. M Jetness (M Y Y ) Undertone () Start Powder, 4 40 C Paste, 4 40 C TABLE 5 Waterborne 1K PU system with binder-free mill base. Binder-Free Mill Base K PU Binder System Raw Material Weight (g) Raw Material Weight (g) Water 44.5 Alberdingk U9800 (35%) 75.8 Tego Dispers 760W (35%) 36.0 Butyl glycol 13.0 Tego Foamex Water 10.0 DMEA 0.5 BYK XPB 255 carbon black 15.6 Tego Wet DMEA 0.2 Total Total Wetting additive to carbon black 70% Total quanitity of CB pigment 18% Letdown with 1K PU Binder System Mill base 8.5 1K PU binder system 91.5 Total Total CB pigment concentration 1.5% CB pigment concentration % Floating Behavior (%)

8 High-Performance Pigment Advances Meet Emerging Needs Next, the new plant oil-based pigment was evaluated in an alkyd/melamine baking formulation (Table 9, p. 30). Again the performance of the new pigment was tested versus regular color furnace grades of carbon black. Results of the evaluation appear in Tables 10 and 11 (p. 30). In the alkyd/melamine formulation, PRINTEX Nature exhibited a better appearance overall than the FIGURE 13 Results for gloss and haze of waterborne coatings based on XPB 430. Gloss Gloss Haze Haze Start Powder, 4 40 C Paste, 4 40 C FIGURE 14 Coloristic results of XPB 430 vs. other carbon black pigment powders. M Jetness (M Y Y ) Undertone () Powder 1 Powder 2 Powder 3 XPB 430 FIGURE 15 Gloss and haze results of XPB 430 vs. other carbon black pigment powders. Gloss Gloss Haze Powder 1 Powder 2 Powder 3 XPB Haze traditional carbon black pigments with a higher gloss value and less haze. It also displayed lower viscosity at low and high shear rates. Coloristic performance of the new pigment more closely resembled that of traditional carbon black pigment in the alkyd/melamine formulation, both in jetness and undertone. However, the traditional carbon black pigments did display higher tint strength in this formulation (Figures 8 and 9, p. 26). The final test formulation for PRINTEX Nature was a 1K waterborne polyurethane formula (Table, p. 30). As with the other systems, XPB 440 was evaluated versus three standard regular color furnace grades of carbon black. Tables 13 and 14 (p. 31) outline the masstone, tint, appearance and viscosity of the formulas. nce again XPB 440 displays similar performance to the standard carbon black pigments. Figures 10 and 11 (p. 26 and 28) display the masstone and tint data of the test samples. Easy-To-Disperse for Top-Quality High-Jet Waterborne Systems Pigment powders typically require thorough dispersion to achieve satisfactory development of coloristic properties. Carbon blacks are considered some of the most difficult to disperse in waterborne systems. ne of the most common requests is for carbon black pigments that only require high-speed mixing to disperse. With this in mind, rion Engineered Carbons developed XPB 430, a dry dispersion of carbon black with the following advantages over traditional products: Easy-to-disperse in water providing very stable pigment pastes within minutes; No milling or further wetting additives needed; Easy to handle free-flowing powder (carbon black pigment conc. = 52.6%); Excellent pigment stabilization providing higher jetness levels combined with a strong bluish undertone; Broad compatibility with most commonly used waterborne binder systems. TABLE 6 2K polyurethane mill base and letdown. Mill Base Formula Weight, g Degalan VP 4157 (60%) Butyl acetate Carbon black Letdown Formula CB mill base from above Degalan VP 4157 (60%) Solvent reducer Desmodur N75 MPA (75%) 6.0 Carbon black concentration 5% Binder concentration 45% CB pigment/binder solids 2.2%

9 TABLE 7 Coloristic and viscosity properties of similar carbon black pigments in a 2K polyurethane system. 20 Viscosity Viscosity 800/s M Pigment Y Haze Gloss 80/s (mpas) (mpas) PRINTEX Nature PRINTEX PRINTEX PRINTEX TABLE 8 Tint behavior of similar carbon black pigments in a 2K polyurethane system. Pigment Ratio Ti 2 :PB GY Rub ut GY Non Rub ut Floating Behavior (%) Relative Tint Strength (%) PRINTEX Nature 100: PRINTEX : PRINTEX : PRINTEX : TABLE 9 Alkyd/melamine mill base and letdown. Mill Base Formula Weight (g) Alkydal F310 SN 60% Shellsol A Carbon black Letdown Formula CB millbase from above Alkydal F310 SN 60% Maprenal MF 805/ EB solvent 17.5 Carbon black concentration 5% Binder concentration 45% Alkyd:Melamine ratio 70:30 CB pigment/binder solids 2.2% TABLE 10 Coloristic properties and viscosity of similar carbon black pigments in an alkyd/melamine system. 20 Viscosity Viscosity M Pigment Y Haze Gloss 80/s (mpas) 800/s (mpas) PRINTEX Nature PRINTEX PRINTEX PRINTEX TABLE 11 Tint behavior of similar carbon black pigments in an alkyd/ melamine system. Pigment Ratio Ti 2 :PB GY Rub ut GY Non Rub ut Floating Behavior (%) Relative Tint Strength (%) PRINTEX Nature 100: PRINTEX : PRINTEX : PRINTEX : XPB 430 can be dispersed directly in water and develop the final coloristic properties within 5 to 10 min. A typical waterborne binder-free paste formulation for XPB 430 is shown in Table 15 (p. 31). A paste with 13% carbon black pigment is prepared by mixing water, defoamer and XPB 430 using a dissolver for 10 min. There is no need for intensive milling or addition of further wetting additives. The viscosity of the obtained paste is low. Fineness of grind is below 10 µm. Storage stability tests were conducted on XPB 430 powder and the paste based on XPB 430 after storage at 40 C (104 F) for four weeks. No visual or measurable change in the quality could be detected with the dry dispersion powder or the paste. Final coatings with a carbon black concentration of 1.5% (typical for automotive) were prepared using a commercially available 30% PU dispersion (Alberdingk U710, Alberdingk & Boley GmbH). The coatings were applied on glass plates (0 μm wet), flash-off for 15 min and force dried at 80 C (175 F) for 30 min. The coloristic and appearance results are shown in Figures and 13 (p. 28 and 29). All of the coatings provided the highest level of jetness (M Y of 325 to 330), a strong bluish undertone, high gloss and low haze. No change in the coloristic properties was obtained after storage, evidence of perfect stabilization of the carbon black pigment in the preparation as well in the paste and final coating. Figures 14 and 15 (p. 29) show the coloristic results of XPB 430 in comparison to several other commercially available high-jet carbon black pigment powders. In order to improve the dispersion quality of the traditional carbon black pigment powders and to stabilize the waterborne mill bases, 90% active wetting agent was used and milled with zirconium beads. (The XPB 430 did not require milling.) The concentration of the carbon black pigments in binder-free mill bases was 13%. Final coatings with a carbon black concentration of 1.5% were prepared TABLE 1K waterborne polyurethane mill base and letdown. Mill Base Formula Weight (g) Water Tego Dispers 760W, 35% Tego Foamex DMEA 0.13 CB171 carbon black 13.0 Letdown Formula CB mill base from above 11.5 Klarlack #3 RL 10103/KB Total Carbon black pigment concentration 1.5%

10 High-Performance Pigment Advances Meet Emerging Needs TABLE 13 Coloristic properties and viscosity of similar CB pigments in a 1K waterborne polyurethane system. Pigment M Y 20 Gloss Haze Viscosity 80/s (mpas) Viscosity 800/s (mpas) PRINTEX Nature PRINTEX PRINTEX PRINTEX TABLE 14 Tint behavior of similar carbon black pigments in a 1K waterborne polyurethane system. Pigment Ratio Ti 2 :PB GY Rub ut GY Non Rub ut Floating Behavior (%) Relative Tint Strength (%) PRINTEX Nature 100: PRINTEX : PRINTEX : PRINTEX : TABLE 15 Recommended paste formula for XPB 430. Raw Material Weight (g) Water 74.8 BYK XPB 430 (52.6% CB) 24.7 Carbon black pigment concentration 13% ph value s s -1 6 using a commercially available 30% PU dispersion (Alberdingk U710, Alberdingk & Boley GmbH). XPB 430 provides high-gloss, low-haze coatings with the highest jetness values combined with very strong bluish undertones. The coloristic properties outperform even the best and extremely well stabilized competitive carbon black pigment powders stabilized with 90% active wetting agent. Conclusion Environmental coatings and the overall greening trend of the global coatings industry will continue to boost the demand for advanced waterborne systems. New high-performance carbon black pigments can offer a balance of properties including ready dispersion and coloristic properties to address emerging needs for coating, ink and polymer formulations. n Aknowledgements Dr. Ariane Adolf, Dr. Kai Krauss, Christof Schilling and Thomas Weprich, rion Engineered Carbons GMBH, Hanau-Wolfgang, Germany. References 1 Lippol-Lohmer, K. Farbe und Lack, (1986), TI 04, Method for Measuring Blackness of Pigment Blacks, Degussa (2001).

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12 The Americas rion Engineered Carbons LLC 4501 Magnolia Cove Drive Suite 106 Kingwood, TX USA phone fax Europe / Middle East / Africa rion Engineered Carbons GmbH Hahnstrasse Frankfurt am Main Germany phone fax EMEA-Pigments@orioncarbons.com Asia / Pacific rion Engineered Carbons Trading (Shanghai) Co., Ltd. Room , BM InterContinental Business Center 100 Yutong Road, Shanghai P. R. China phone fax APAC-Pigments@orioncarbons.com All information and statements contained herein are believed to be accurate, but rion Engineered Carbons LLC, its agents and/or affiliates make no warranty with respect thereto, including but not limited to any results to be obtained or the infringement of any proprietary right. Improper and unauthorized use or application of such information or statements or the material or systems described herein is at user s sole discretion and risk, and consequently user acknowledges that rion Engineered Carbons LLC shall bear no responsibility or liability for same. Nothing herein shall be construed as a license of or recommendation for use which infringes any proprietary right. All sales are subject to rion Engineered Carbons LLC s Standard Terms and Conditions of Sale, including but not limited to its Limited Warranty rion Engineered Carbons LLC EC /2014