Trolling for New Technology: ANTEC 2013

By Jan H. Schut

New technologies at ANTEC 2013, the Society of Plastics Engineers (SPE) Annual Technical Conference in Cincinnati, OH, April 21-24 include the first “fractal structuring” of co-injected polymers not just into layers, but into geometric patterns of almost unlimited complexity. The technology comes from the Technical University of Eindhoven in the Netherlands (www.mate.tue.nl) and is the first 3-D structuring of any molded part. A new rheometer presented by Clemson University (www.clemson.edu) also creates and tests coex 3-D patterns for extrusion, using chaotic advection with independently turning stir rods–the only other known 3-D structuring.

Compounding news includes the first ultrasonic twin-screw extruder from the University of Akron in Ohio (www.uakron.edu), allowing comparison to ultrasonic single-screw extrusion and ultrasonic dies. South China University of Technology in Guangzhou (en.scut.edu.cn) reports a new co-rotating triple-screw extruder with vibrating middle screw, built by Guangzhou POTOP Experimental Analysis Instrument Co. Ltd. in China (www.potop-lab.com), a spin-off of the university, represented by Harden Industries Ltd., Hong Kong (www.hardenmachinery.com).

New materials include shape memory polymers with a range of temperature triggers and new biopolymer blends with polybutylene succinate (PBS), an emerging biopolyester. As five ventures around the world build plants to make bio succinic acid monomer for PBS, new PBS blends are timely (see this blog April 26, 2012). In biomaterials, soy and bone meal polymers show unusual benefits in pots and films for agriculture—as they degrade, they feed plants.

The letter and number in brackets after the title of a paper or poster indicate the day of the week and session when that paper was given, i.e. [T12] was session 12 on Tuesday, April 23. For people who didn’t attend ANTEC, all papers are available on CD from the SPE (www.4spe.org) for $200 to members and $250 to non-members. Student posters aren’t on the CD unless they were also presentations, so referenced posters not on CD are linked below.

‘STRUCTURING’ AND OTHER INJECTION MOLDING NEWS

Fractal Structuring in Polymer Processing [Plenary Speaker] by Han Meijer, professor of mechanical engineering & materials technology at Eindhoven Technical University in the Netherlands (www.mate.tue.nl). Flat tool halves with serpentine flow paths on the parting surfaces, similar to a static mixer, co-inject polymers into complex internal patterns. Patterns are made by cutting, rotating and combining horizontal and vertical stratified elements formed between the flat mold halves. The patterns are then preserved without compression in special runners into the mold. Meijer developed and verified the tooling using two colors of epoxy at room temperature before molding them with thermoplastics.

Eindhoven Technical University "fractal structuring"

Eindhoven Technical University’s “fractal structuring” creates serpentine flow between flat mold halves to make complex geometries like layers perpendicular to a part surface and “tree” shapes with trunks, branches, twigs and leaves–the first repeatable 3-D structures in molded parts.

Fractal structuring can make repeatable 3-D patterns for the first time, including layers perpendicular to a part surface and “tree” shapes with trunk, branches, twigs, and leaves. “Extension to multiple trees with many branches in a forest is potentially possible, but here only making of one tree with 65,000 leaves is demonstrated,” Meijer explains modestly, adding that “compression of stratified structures is to be avoided.” The technology is also being developed for coextrusion, working with ETH Zurich University in Switzerland (www.ethz.ch).

2 PC-Recu-Module for Energy Recovery with Hydraulically Driven Injection Molding Machines [W11] by Marco Lenzen, Universitaet Duisburg-Essen in Germany (www.uni-due.de).  A new “2 Plates Clamping Recuperation” hydraulic module is designed and simulated with a drive, three accumulators, valves, and controls. It’s expected to recover up to 50% of the energy typically lost in hydraulic clamping. The first prototype is being built now.

Dynamic Uni-Layer Melting Model [W11] by Trevor Spika, Spiral Logic Ltd., Hong Kong, China (www.spirallogic.com.hk). Spiral Logic’s unusual new injection screw and T-Rex barrel melt without a compression zone, boasting shorter residence and cooler temperature than conventional screws. Introduced at NPE 2012, the screw is shown for the first time at ANTEC.

Spiral Logic injection screw

Spiral Logic introduced an unusual injection screw with 1:1 compression ratio at NPE 2012, but didn’t show the 14:1 screw until ANTEC. The screw was tested using a special windowed T-Rex barrel and reportedly melts faster at cooler temperatures than conventional screws.

An Investigation of Vibration-Assisted Injection Molding Manufactured Polymer Material and the Effect of Molecular Orientation on Biodegradation Activity [T12] by Qi Li, Lehigh University, Bethlehem, Pa. (www.lehigh.edu). PLA medical devices molded with more vibration-induced molecular orientation degrade more slowly in the body than ones with less orientation. Software controls vibration by opening and closing valves on the hydraulic screw.

EXTRUSION NEWS

A Device for Simultaneous In-Situ Structuring and Measurement of Rheological Properties of Polymer Blends and Composites [T20] by David Zumbrunnen, S. Ramaswami, Clemson University, Clemson, S.C. (www.clemson.edu). This rheometer creates 3-D internal patterns by chaotic advection, and then measures their properties in situ. Chaotic advection uses rotating stir rods in a barrel to blend polymers into repeatable structures for blown and cast film.

Thermal and Morphological Behavior of PLA/PBS/CSW Blends Processed by Vane Extruder [Poster #1559206] by Rong-yuan Chen, South China University of Technology, Guangzhou (en.scut.edu.cn). PLA and PBS are blended with 5% calcium sulfate whiskers on a revolutionary new vane extruder invented at the university. The vane extruder, which elongates melt, was introduced at ANTEC last year (see this blog April 2012).

3D-CFD Simulation of Polymer Plastification in a Single-Screw Extruder Under High-Speed Conditions [M8] by Gregor Karrenberg, Johannes Wortberg, University of Duisburg-Essen in Germany (www.uni-due.de). This simulation of a 35-mm screw with a transition section depth going from 6 mm to 2 mm, extruding LDPE at up to 2000 rpm, shows high-speed extrusion melts without a melting mechanism.

A Mechanism for Solid Bed Break-up in Single Screw Extruders [T27] by Gregory Campbell, Clarkson University, Potsdam, NY (www.clarkson.edu); Mark Spalding, Dow Chemical Co., Midland, MI (www.dow.com).  A fresh look at solid bed melting in a conventional screw finds that screw rotation physics carries melt under the solid bed, creating flow and pressure that breaks up the bed. The authors have a new book and photos to prove it.

NEW SHAPE MEMORY MATERIALS

Tunable Shape Memory Polymers Based on Compounds of Ionomers and Fatty Acids [New Technology Forums] by Robert Weiss, Jing Dong, Ying Shi, and Rostyslav Dolog of the University of Akron (www.uakron.edu). Instead of synthesizing a new polymer for every switching temperature, this technology blends an ionic polymer and fatty acid or fatty acid salt with the desired melting point. A patent-applied-for blend of sulfonated PEEK ionomer and fatty acid salt (U.S. Pat. Applic. # 20080287582) could be the first high temperature (>300 °C) thermoplastic shape memory polymer.

Thermoplastic Elastomers with Thermally Induced Shape-Memory Effect [New Technology Forums] by Liang Xu and Krishna Venkataswamy from the GLS Thermoplastic Elastomers division of PolyOne Corp., McHenry, IL (www.glstpes.com). This patent-applied-for (WO Pat. Applic. # 2012/166782) combination of a maleated styrenic block copolymer and polycaprolactone shows “manageable” shape memory characteristics.

Injection Molding of Novel PLA/Thermoplastic Polyurethane Blends with Shape-Memory Behavior [W10] by Xin Jing, Bionates Wisconsin Institute for Discovery, University of Wisconsin, Madison, WI (wid.wisc.edu). A 70/30 blend of PLA and TPU deforms into temporary shapes at room temperature, then recovers its original shape “fairly quickly” at glass transition temperature. It’s believed to be the first PLA/TPU blend with shape memory.

ULTRASONIC TWIN- AND TRIPLE-SCREW COMPOUNDING NEWS

Preparation and Properties of Polyetherimide (PEI)/Graphite Composites with Ultrasound Assisted Extrusion [M6] by Jing Zhong, University of Akron (www.uakron.edu). A new ultrasound-assisted twin-screw extruder improves electrical conductivity of PEI/expanded graphite composites.

Continuous High Power Ultrasonic Extrusion of PEEK-CNT Nanocomposites [M4] by Todd Lewis, University of Akron (www.uakron.edu). The new ultrasonic twin-screw extruder mixes PEEK with only 1% carbon nanotubes and gets 16% higher tensile modulus and three times higher electrical conductivity.

Ultrasonic Devulcanization of Tire Rubber of Different Particle Sizes in Twin-Screw Extruder [M6; also Poster # 1657660] by Tian Liang, University of Akron (www.uakron.edu). The patent-applied-for ultrasonic twin-screw (WPO # 2012142562) devulcanizes 10- and 30-mesh rubber particles at 40 kHz, with more devulcanization and fewer gels for the smaller 30-mesh size. Revulcanized 30-mesh rubber also has higher elongation at break and tensile strength.

University of Akron ultrasonic horn

The University of Akron added an ultrasonic horn to the first twin-screw extruder–a 16 mm micro compounder—allowing comparison to compounded, devulcanized and decrosslinked material from ultrasonic single-screw extruders and ultrasonic dies.

Decrosslinking of Crosslinked HDPE via Ultrasonically Aided Extrusion [W7] by Keyuan Huang, University of Akron (www.uakron.edu). Decrosslinking increases with ultrasonic amplitude in both single- and twin-screw extruders, but mechanical properties of HDPE are better from the ultrasonic single-screw. This is the first reported comparison of materials from ultrasonic single- and twin-screw extruders.

Preparation and Microcellular Foaming Investigation of PLA/Talc Composites [M19] by Peng Xiang-Fang, South China University of Technology in Guangzhou (en.scut.edu.cn). A new 22 mm, 40 L/D triple-screw extruder and patent-pending foaming device are used to make this bio composite with CO2 blowing agent. The triple-screw extruder is built by Guangzhou POTOP Experimental Analysis Instrument Co. Ltd. in China (www.potop-lab.com).

South China University triple-screw extruder

South China University of Technology reports R&D with a new co-rotating triple-screw extruder with vibration on the middle screw, built by Guangzhou POTOP, a 2009 spinoff from the university. POTOP’s lab extruders are represented by Harden Industries Ltd. in Hong Kong.

Preparation and Characterization of Poly(lactic acid)/Poly(vinyl alchohol) Blend [P2] by Peng Yu, South China University of Technology in Guangzhou (en.scut.edu.cn). POTOP’s new triple-screw extruder (www.potop-lab.com) is used to make more biopolymer blends.

 

PBS BLENDS AND OTHER BIO MATERIAL NEWS

Mechanical Properties and Crystallization of Talc-Filled PLA/Poly(butylene succinate) Blend Composites [T1] by Weraporn Pivsa-Art, Rajamangala University of Technology Thanyaburi, Thailand (www.eng.rmutt.ac.th). Blending up to 30 wt % PBS and up to 20% talc into PLA improves PLA’s tensile modulus, crystallinity, and impact strength.

Effect of Poly(butylene adipate-co-terephthalate) Contents on Crystallization and Mechanical Properties of Polymer Blends of PLA and Poly[(butylene succinate)-co-adipate] [T1] by Sommai Pivsa-Art, Rajamangala University of Technology Thanyaburi, Thailand (www.eng.rmutt.ac.th). Adding up to 50% PBAT to an 80/20 blend of PLA and PBSA also increases crystallization and improves properties.

The Role of Surface Interactions in Renewable Poly(butylene succinate)-Silica Nanocomposites [M21] by Margaret Sobkowicz; Poly(butylene succinate) Fumed Silica Nanocomposite: Functionality and Rheology [Poster # 1628517] by Xun Chen, University of Massachusets Lowell (www.uml.edu). Mechanical properties of PBS improve when it’s blended with fumed silica, whether the silica is surface treated or not.

Mechanical Properties of HDPE/Pennycress Press Cake Composites [M35] by Louis Reifschneider, Illinois State University, Normal, IL (www.ilstu.edu); Rogers Harry-O’Kuru, National Agricultural Utilization Research Center, Peoria, IL (www.ars.usda.gov). HDPE with 25 wt% fibers from Pennycress, a potential new oilseed crop for biodiesel, and 5% coupling agent gets 42% higher tensile modulus, 12% higher tensile strength. Impact strength drops 15%.

Blended Meat & Bone Meal Bioplastic and Polyethylene Sheets: Enhanced Moisture Resistance and Mechanical Properties [T21] by Sam Lukubira, Clemson University, Clemson, SC (www.clemson.edu). Cross-linking plasticized bone meal polymer and blending with LLDPE makes moisture-resistant film with potential for composite seed germination mats.

Sustainable Materials for Horticultural Application [T21] by Gowrishankar Srinivasan, Iowa State University, Ames, IA (www.iastate.edu). Plants grown in soy polymer/PLA pots grow better than plants grown in PP or natural fiber pots. Apparently, as soy polymer degrades, it feeds the plants, while the soy polymer/PLA blend retains moisture. The university reported this in a symposium in 2012, but ANTEC was its first public presentation.

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Simply Brilliant

By Jan H. Schut

Imagine molding plastic with no energy cost – zero, zip, nadda, as the saying goes. Karl von Kries, CEO of startup LightManufacturing LLC (www.lightmanufacturingsystems.com) in Pismo Beach, CA, has done just that. He’s invented the world’s first solar-heated plastic molding and is launching solar-heated rotational molding commercially this month at SPE’s GPEC (www.sperecycling.org) conference in New Orleans, LA, on March 20-22. The patent-applied-for technology (U.S. Pat. Applic. # 20120104658) was first presented last November at the Association of Rotational Molders conference in Minneapolis, MN.

Don’t confuse von Kries’s approach with using solar electric power to mold, which has been done before. Penninsula Packaging (www.penpack.com) in Exeter, CA, generates about a third of its power for sheet extrusion and 14 thermoforming machines with a field of hundreds of solar panels. Instead von Kries concentrates sunlight directly onto molds to melt and mold the plastic. Cycle time is only slightly longer than conventional rotomolding, he says—25 minutes vs. 19 minutes for the same part. “We’re seeing now how much faster we can go,” he says. “If we add more Heliostats, we think we can drop cycle time a lot.”

Also at GPEC, two new environmentally friendly materials will be introduced: “hyperbranched” recycled PLA with melt strength better than, or comparable to, virgin PLA by Interfacial Solutions (www.interfacialsolutions.com), a contract R&D firm in River Falls, WI, and new developmental 25% to 50% starch-filled soft elastomers down to 55-65 Shore A from bio-plastic compounder Cereplast Inc. (www.cereplast.com), El Segundo, CA.

THE ICARUS FACTOR

LightManufacturing’s game-changing solar rotational molding machinery is built into a shipping container. It needs no building, electrical hook up, or even concrete pad. The container can be deposited on flat ground or in a customer’s parking lot (anywhere there’s enough sun) and mold parts closer to where they’re needed. It can’t run at night, and it can’t run in many parts of the country, but von Kries figures it will work on almost half of the earth’s land surface, certainly throughout the South and Southwest United States.

LightManufacturing Rotomolding Machine

LightManufacturing’s solar rotomolding machine is built into a shipping container, so it needs no building, electrical hook up, or concrete pad. This isn’t solar-generated electric power.
Molds are heated directly by radiant heat from sunlight.

In the early ‘90s, von Kries worked in engineering and new product development at rotational molder Hardigg Industries Inc. in South Deerfield, MA, now part of Pelican Products Inc. (www.pelican.com), Torrance, CA. In 1994, he took a project for portable sound equipment for the military and spun it off as a separate company, called Technomad LLC (www.technomad.com) with offices in Boston, MA, of which von Kries is still CEO.

Technomad’s audio products were housed in rugged ¼ to 3/8-inch-thick, rotomolded medium density PE cases, molded by Hardigg. von Kries moved to California in 2005 and saw solar mirrors, or heliostats, heating steam turbines with reflected sunlight. He got the idea to heat rotational molds that way, too, saving a lot on energy. By 2009, he set up LightManufacturing with investors and was designing the first solar-heated roto-molding.

He started using commercially available heliostats, but the supplier went out of business. So he and his team spent two years designing their own heliostats, which he says are the lowest cost per reflected watt on the market—2,000 watts of heat for about $1,400, or $1.60 per watt. The firm’s H1 Heliostats became a separate product selling to architects and home owners for green home heating.

LightManufacturing designed H1 Heliostats

LightManufacturing designed its own H1 Heliostats out of aluminum coated reflective PET film stretched over a square frame. An array of 20 H1 Heliostats puts 40,000 watts of heat into solar rotational molds. Cycle time is 25 min. vs. 19 min. for conventional rotomolding.

H1 Heliostats are 2.3 square meter mirrors made of aluminum-coated PET film stretched over a frame. The reflective film has a threaded rod on the back that adjusts the mirror shape to focus light on a larger or smaller area to fit mold size. “If you walk around in the beams of light, which I do all the time, they feel like a strong space heater,” von Kries explains. Heliostats can stand 20 mph steady wind and gusts to 60 mph, or up to 95 mph in “safe position” sideways to the wind, LightManufacturing says. If they’re damaged, it’s relatively easy to replace the reflective film.

MOVE HEAT, NOT MOLDS

Solar molds aren’t mounted on massive articulated arms on a central rotor and moved in and out of a convection oven like conventional rotomolding. The solar rotational molding machine has two chambers, each with a molding station and a large Lexan polycarbonate window on one side to let light in. Solar-heated molds rotate on two axes, but in fixed position.

Twenty heliostats are assembled and installed in an array in front of the windows to direct sunlight first onto one mold, then onto the other, while the first mold cools. Radiant heat from sun light goes into the mold without heating the surrounding air or the framework holding the molds, so cooling is faster than with conventional molding, von Kries says. Temperature inside the molding chamber reaches only about 180 degrees F compared to 500 degrees F in a gas-fired convection oven for conventional rotational molding.

The solar machine uses standard aluminum or steel molds up to 48 in. on the diagonal, coated with black heat-absorbing material. Optional wireless thermocouples can provide real-time temperature data. Solar panels installed on top of the enclosure power motors, cooling fans and electronics.

LightManufacturing now has 10 employees and several solar rotational molding machines in beta test sites in the U.S. for over 18 months, producing parts commercially for Technomad and other customers. They have molded medium density PE and LLDPE, but haven’t yet tried PP or high heat materials like nylon. A turnkey system costs “well under” $100,000, von Kries says, including two molding stations, 20 H1 Heliostats, two photovoltaic panels, and wireless computer controls. A conventional rotational molding machine with a convection oven costs around $300,000.

Because solar rotational molding runs off-grid, it could be attractive in third world markets or for disaster relief, molding things like water tanks or sectional emergency housing without needing outside power. But von Kries argues that the competitive advantage is most compelling in a developed market with high energy costs. “Once a few companies have it, they’ll eat the competition,” he predicts.

“Rock-and-roll” type rotational machines with multiple arms could be adapted to solar heat using “a single large horizontal window,” von Kries says, “and large parts could be molded in site-assembled enclosures, instead of the shipping container approach.” Direct solar heat could also be applied to other molding processes by putting solar arrays onto factory roofs and using light pipes to bring radiant heat into the building. Thermoforming and compression molding could be adapted fairly easily to solar heat, he thinks: “Those are the next things we’re going to look at.”

NEW RECYCLED PLA, NEW SOFTER STARCH-FILLED ELASTOMERS

Interfacial Solutions’ technical director, Adam Pawloski, is introducing new post-consumer and post-industrial recycled PLA compounds at GPEC, made with the company’s reactive process for hyperbranching PLA. Interfacial introduced its patent-applied-for hyperbranching chemistry (International Pat. Applic. # WO 2010/1080760 A2) five years ago in compounds with virgin PLA to improve melt strength for durable applications and extrusion without a penalty for processability. Hyperbranching is now being used with scrap PLA to improve mechanical properties “to meet or exceed those of virgin PLA,” Pawloski says.

Hyperbranching adds lots of short chains onto linear PLA molecules, increasing melt strength without increasing viscosity and die pressure, according to tests done by the Macosko group at the University of Minnesota (research.cems.umn.edu) in Minneapolis, MN. This gives hyperbranching an advantage compared to several commercial chain extending additives for PLA like CESA-extend masterbatches from Clariant Corp. (www.clariant.com), Charlotte, NC and Joncryl ADR from BASF Group (www.basf.com) in Germany, which increase PLA’s melt strength, but also increase shear viscosity and die pressure.

Interfacial Solutions hyperbranched PLA

Linear PLA has poor melt strength and high viscosity, making extrusion difficult. Chain extenders add a few long chains, which raise melt strength, but also raise viscosity and pressure. Hyperbranching adds short chains, improving melt strength without hurting processability.

Interfacial is commercializing several new grades of hyperbranched post-industrial recycled PLA in its “de Terra bio-based polymer” product line. For the new recycled PLA grades, Interfacial tested reclaimed PLA from eight post-industrial and one post-consumer source and reports this data as well. Post-industrial sources tested include mixed reground card stock, recycled water bottles and cups, and recycled reground gift cards. Properties of the scrap materials, especially melt flow index and impact strength, vary widely, but can be adjusted using hyperbranching to meet the needs of an application. Interfacial will make custom recycled PLA on a toll basis for customers or license its technology for companies to use in-house.

Interfacial Solutions PLA blends

Interfacial Solutions tested “Gen I” and “Gen II” blends of recycled and reprocessed PLA with low and high initiator (INT) and low and high hyperbranching (CXL). Note how MFI decreases while molecular weight increases with more hyperbranching.

Cereplast’s chief technology officer Kelvin Okamoto is introducing softer starch-filled elastomers than the company has presented before. Its patent-applied-for (U.S. Pat. Applic. # 20090048368) starch-content elastomers were introduced at NPE 2012 last March in Orlando with two grades, Hybrid 111D with 25% starch and Hybrid 112D with 50% starch. Both elastomers, however, only go down to 85-95 Shore A in softness for injection molded applications like soft-grip handles and soft-touch automotive parts.

Base Resin TPE1 TPE1 TPE2 TPE3 EA1
Starch Content % 25 50 25 25 25
Density g/cc 0.96 1.08 0.98 0.98 1.00
Melt Flow g/10′ 7.3 3.2 0.4 25.0 9.7
Tensile Strength @ Yield MPa 4.4 5.7 4.2
Tensile Elongation % >450 440 245
Flex Modulus MPa 16 51 30
Gardner Impact J 14.2 15.9 12.1
Taber Abrasion WI 56 144 117
Shore Hardness A 80 93 55 65 88

Cereplast is introducing new 25% starch-filled TPEs as soft as 55-65 Shore A hardness and thinks the elastomers can be made even softer–down to 30 Shore A–still with 25% starch.

Cereplast has since developed even softer elastomers with 25% starch down to 55-65 Shore A hardness in a range of melt flow indices for injection molding and extrusion applications. These softer elastomers don’t have commercial grade names yet, but are available for testing. Cereplast’s Okamoto believes they can go even softer–down to a 30 Shore A.

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How Shale Gas Is Changing Propylene

By Jan H. Schut

North American shale gas is reshaping petrochemicals. Two plenary speakers at the Society of Plastics Engineers’ International Polyolefins Conference 2013 in Houston, TX, in February describe some of the impacts. Tim Roberts, vice president at LyondellBasell (www.lyondellbasell.com) presents “Potential of Shale Gas for the Petrochemical Sector,” and Srivatsan Iyer, vice president of finance, planning, and strategy at Braskem (www.braskem.com) presents “North American Energy Transformation and Impact on Petrochemicals.” Videos of their plenary speeches are available to non-attendees for $50 (www.spe-stx.org/conference).

The big change for plastics processors is the first “on purpose” propylene plants in North America, which could make U.S. propylene the cheapest in the world. Here’s why: 90% of propylene is still made as a by-product of cracking for ethylene and gasoline. But the mixture fed to crackers in North America is changing with less naphtha from crude oil and more ethane from natural gas.  In 2005, 30% of feedstock for cracking was naphtha and 70% ethane, according to research firm ICIS (www.icis.com) in Houston. By 2012 only 12% was naphtha and 88% ethane.

Braskem Plenary speakers

Plenary speakers at SPE’s Polyolefins Conference analyzed shale gas’s impact on plastics, especially propylene. New plants using PDH (propane dehydrogenation) to make “on purpose” propylene could make North American propylene the least expensive in the world.

Ethane yields much less propylene, so the feedstock shift caused a 40% drop in U.S. propylene production from 13 billion pounds in 2005 to only 7.6 billion pounds in 2012. That 5.4 billion pound shortfall is driving a wave of new “on purpose” propylene plants. In the U.S. the feedstock will be propane. In China, the feedstock is refinery gas oil and methanol from coal. In Brazil, India, and elsewhere it’s waste biomass like sugar cane bagasse, wood scrap, and paper mill waste.

“ON PURPOSE” PROPYLENE FROM PROPANE

In the past year six new plants were announced in North America to make “on purpose” propylene from propane by a previously little used process called propane dehydrogenation (PDH). PDH removes two hydrogen atoms from propane (C3H8), converting it to propylene (C3H6). PDH chemistry isn’t new. The first plant was built in 1990 at National Petrochemical Co. in Thailand (now PTT Public Co.), a state-owned oil company, using the Oleflex process from Universal Oil Products, now UOP LLC (www.uop.com), part of Honeywell.

But PDH is a niche that only works where propane is cheap and propylene expensive. UOP has five more PDH units in Asia and four integrated with propylene production in Saudi Arabia at Advanced Petrochemicals Co. (www.advancedpetrochem.com), Al-Waha Petrochemicals Co., and Saudi Polyolefins Co. (www.tasnee.com) in Al-Jubail and at National Petrochemical Co. in Yanbu. Al-Waha and Saudi Polyolefins are joint ventures with LyondellBasell, which markets the propylene.

In the past the price of propylene and propane were so close in the U.S. that it wasn’t cost effective to dehydrogenate propane, but now with low cost propane from shale gas, it is. Petrologistics L.P. (www.petrologistics.com) in Houston started up the largest PDH plant in the world (544,000 metric tons/year) in 2010 and announced a second plant of the same size to start in 2017, both using Catofin PDH technology from Lummus Technology Inc., Houston, part of Chicago Bridge and Iron Co. (www.cbi.com).

Petrolgostics

In 2010 Petrologistics started the world’s largest PDH plant, making propylene directly, rather than as a small by-product of cracking for ethylene or gasoline. Petrologistics is the first of seven new PDH plants announced in North America.

Enterprise Products Partners L.P. (www.enterpriseproducts.com), Houston announced plans for a 750,000 metric ton/year PDH plant in Houston to start in late 2015, also using Lummus’s Catofin technology.

Dow Chemical Co. (www.dow.com), Midland, MI, announced plans for a 750,000 metric ton/year PDH plant in Freeport, Texas, to start in 2015 using UOP’s Oleflex PDH technology.

C3 Petrochemicals, an affiliate of Ascend Performance Materials LLC, a maker of polymer and fiber in Houston, requested permits for a new PDH plant at Ascend’s site in Chocolate Bayou to start in late 2015 using UOP’s PDH technology.

Taiwan-based Formosa Plastics Corp. U.S.A. (www.fpcusa.com), Livingston, NJ, announced plans for a 600,000 metric ton/year PDH plant in Point Comfort, Texas, to start in 2016. Sasol Ltd. (www.sasol.com) in South Africa is doing the feasibility study.

The Williams Companies Inc. (co.williams.com), Tulsa, OK,  are planning Canada’s first PDH plant, a 500,000 metric ton/year plant in Redwater, Alberta, to start in 2018, using a PDH process designed by Fluor Corp. (www.fluor.com), Irving, TX.

“ON PURPOSE” PROPYLENE FROM GAS OIL AND METHANOL

Propane isn’t the only route to “on purpose” propylene. In China, dozens of new plants are being built to use gas oil and coal.  Decades ago the Sinopec Research Institute of Petroleum Processing (www.ripp-sinopec.com) in Beijing invented a process called Deep Catalytic Cracking, using a zeolitic catalyst with gas oil in a conventional Fluid Catalytic Cracker, producing more propylene and less gasoline than conventional cracking.

There are seven Deep Catalytic Cracking plants currently operating or under construction in China, and one outside of China. Thailand Petrochemical Industries in Rayong, Thailand, started a Deep Catalytic Cracking plant in 1997, designed by Technip Stone & Webster Process Technology (www.technip.com), Stoughton, MA, with Sinopec’s process. Then Shaw Group Inc., Baton Rouge, LA, acquired recently by Chicago Bridge & Iron (www.cbi.com), had the exclusive license for Deep Catalytic Cracking outside of China and reportedly licensed 16 more plants. The Deep Catalytic Cracking license was sold to Technip last year.

Shenhua model

Shenhua released photos of a model of its historic coal-to-olefins plant in Baotuo, Inner Mongolia, not photos of the plant itself. The process is criticized for high water use in an arid area. Some 20 other plants are planned in China to go from coal to olefins.

More revolutionary are new technologies going from coal to olefins. At least 20 projects for coal-to-olefins or methanol-to-olefins have been reported in China. In 2010, Shenhua Group Corp. (www.shenhua group.com.cn) in Beijing, China, the large state-owned coal company, built the world’s first commercial coal-to-olefins plant at Shenhua Baotou in Inner Mongolia. The historic complex has a 1.7 million metric ton/year coal-to-methanol plant, followed by a 470,000 metric ton/year methanol-to-propylene plant and involved many international engineering partners.

Shenhua and GE Energy (www.ge-energy.com) partnered on the initial coal liquefaction and gasification technology to make syngas. Shenhua and GE also have a 50/50 joint venture since 2012 to develop and license clean liquefaction technology in China. The next stage at Baotou converts syngas (CO2 + H2) into methanol (CH3OH) using “MegaMethanol” technology from Lurgi GmbH (www.lurgi.com) in Frankfurt, Germany, which was recently acquired by Air Liquide in Paris.

Shenhua

The world’s first commercial coal-to-olefins plant started up at Shantou Baotou in China in 2010 for 1.7 million metric tons/year. It uses Lurgi’s first methanol-to-propylene reactor for 470,000 metric tons/year of propylene. Photo: Toby Smith/Circle of Blue

Next comes the world’s first commercial methanol-to-propylene plant. This uses Lurgi’s new MTP technology with a multi-stage fixed bed reactor and steam dilution to convert methanol (CH3OH) selectively into propylene with gasoline as a by-product. Lurgi now has a second MTP plant operating at Datang International Power Generation Corp. (www.dtpower.com) in China , and a third under construction, also for Shenhua.

Other petrochemical companies have new methanol conversion technologies too. UOP and INEOS Group (www.ineos.com), formerly Norsk Hydro, developed an MTO (methanol-to-olefins) technology to convert methanol from coal into both propylene and ethylene, using SAPO-34 catalyst. They have sold three licenses in China: Wison (Nanjing) Clean Energy Co. Ltd. for 295,000 metric tons/year to start this year; Shandong Yangmei Hengtong Chemicals Co. Ltd for 295,000 metric tons/year to start in 2014; and Jiutai Energy (Zhungeer) Co. for 600,000 metric tons/year. UOP and Total Petrochemicals S.A. (www.totalpetrochemicals.com) in France  have a demonstration MTO plant in Feluy, Belgium, since 2009.

UOP/Total

UOP and Ineos have new methanol-to-olefins technology to make coal-based methanol into propylene and ethylene and have sold three licenses in China. UOP and Total have set up a demo MTO plant in Feluy, Belgium, since 2009. Photo: Total-Visual News

Sasol Ltd. (www.sasol.com) in South Africa; KBR Inc. (formerly Kellogg Brown and Root) (www.kbr.com) in Houston; Axens S.A. (www.axens.com), Rueil-Malmaison, France, partnering with Headwaters Inc. (www.headwaters.com), South Jordan, UT; and SK Innovation Co. (eng.skinnovation.com) in South Korea also offer coal-to-liquids or methanol-to-olefins technologies and have recently built plants or announced licenses or co-licenses in China.

Chemical companies insist that “on purpose” propylene will have to meet the same purity specs as conventional polymer grade monomer. But “on purpose” propylene is made with different feedstocks, different catalysts, and more difficult chemistries. PDH units use propane, which is typically cleaner than naphtha, so propylene from PDH shouldn’t have purity issues. Coal-based olefin processes, however, are new and start with liquefied coal, which has impurities like mercury, arsine, and sulfur. These impurities have to be removed before it’s made into syngas, or they hurt the catalyst in the next methanol reaction. So propylene from gasified coal is more problematic.

The Holy Grail for chemists would be a reaction that goes directly from methane (CH4), the main component of natural gas and the least expensive hydrocarbon, to ethylene for olefins and gasoline. Siluria Technologies Inc. (www.siluria.com), San Francisco, CA, a silicon-valley energy startup, recently announced a patent-applied-for catalyst for “oxidative coupling of methane to ethylene” (U.S. Pat. Applic. # 20120041246 and 20130023709). Siluria used molecular biology to design the catalyst in which a virus is coated with metals to make something like a tangled ball of nano wires. It’s a catalyst approach that has been tried before, but not commercially. This year Siluria plans to start building a demo plant for 1000 pounds/day of ethane. Dow, BP p.l.c. (www.bp.com), and other chemical companies also hold patents on catalysts for methane conversion to olefins, but nothing has been commercialized.

“ON PURPOSE” PROPYLENE FROM BIOMASS

New plants and processes are also in R&D using heat, fermentation, and metathesis to make propylene from biomass, but several projects are either on hold or changing to natural gas-based feedstock. Braskem S.A. (www.braskem.com) in Sao Paolo, Brazil, announced plans in 2010 to build a semi-works 30,000 metric ton/year metathesis plant in Rio Grande do Sul, Brazil, to start up this year. But the plant is delayed because of market conditions, Braskem says.

Metathesis is a difficult chemical reaction that rearranges molecules and is much more complicated than simple cracking of hydrocarbons. Bio-ethylene (C2H4) is first dimerized, or combined in pairs, into bio-butene (C4H8). Then metathesis rearranges the bio-butene (C4H8) and bio-ethylene (C2H4) into bio-propylene (C3H6).

Propylene metathesis was invented by Philips Petroleum Co. in the early ‘60s and used by Shell (the SHOP or Shell Higher Olefin Process) and Lyondell in the ‘80s to make propylene from butene. Lummus bought the rights to Phillips’ metathesis process and uses it in Lummus’s OCT (olefins conversion technology) to make propylene and ethylene.

A Dow/Mitsui Chemical joint venture in Brazil was announced last year to make bio-ethanol from sugar cane into bio-polyethylene, but this venture is also on hold. Dow planned to use dehydration, not metathesis.

Plasma is another potential route to propylene. High temperature plasma is used to gasify biomass, including municipal solid waste and even sewage. Zeus Development Corp., a research firm in Houston, lists hundreds of such gasification projects globally (www.zeusintel.com/Gasification/GlobalGasificationProjectListing.aspx). It’s fascinating reading, but most projects are for power, not plastic.

A few gasification projects, however, have plastic potential. Alter NRG Corp. (www.alternrg.com) in Calgary, Alberta , which owns Westinghouse Plasma, started up a very high temperature (2500 °C) Westinghouse Plasma gasifier at Wuhan Kaidi Holding Investment Co. (www.kaidi-hi.com/en) in Wuhan, China,  to convert 100 tons/day of waste biomass into syngas, which could be converted into methanol and then olefins.

Coskata

Westinghouse Plasma ran tests for two years with biofuel startup Coskata, gasifying wood waste, then fermenting the gases into syngas for biofuels and bio plastics. Coskata, however, strategically switched from biomass to lower cost natural gas feedstock.

Coskata Inc. (www.coskata.com), Warrenville, IL,  a biofuel startup, partnered with Total and IFP Energies Nouvelles (www.ifpenergiesnouvelles.com) in France and ran two years of tests with Westinghouse’s plasma technology to gasify wood waste into syngas and reform natural gas to feed fermentation for biofuels and bioplastics. Coskata shelved IPO plans last year and switched from biofeedstock to natural gas.

Using low temperature plasma, TopLine Energy Systems Inc., Brookville, FL, announced a partnership last year with Maverick Biofuels Inc. (www.maverickbiofuels.com), Research Triangle Park, NC, to integrate TopLine’s PRISM plasma reactor for syngas with Maverick’s chemical process to convert waste biomass into olefins and then into alcohols for biofuel. The bio-olefins could also be used for bioplastics.

Envergent Technologies LLC (www.envergenttech.com), part of Honeywell, a joint venture of UOP (also part of Honeywell) and Ensyn Corp. (www.ensyn.com) in Wilmington, DE, uses pyrolysis to convert forest and agricultural waste into syngas. Envergent has sold one license in Malaysia, but it’s for energy, not plastics.

There is even, in R&D, a direct bio-route to propylene. Global Bioenergies (www.global-bioenergies.com) in Evry, France,  last October claimed to have proven the first process for direct conversion of biomass into propylene by fermentation. The patent-applied-for technology (U.S. Pat. Applic. # 2011165644) uses genetically modified micro-organisms to convert glucose into propylene. But the problem is still cost versus gas.

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When the Going Gets Tough…

By Jan H. Schut

Here’s what some companies in the plastics industry are doing to keep going. We asked senior executives from a dozen companies, including processors, machine builders, and material suppliers, to share their strategies for survival and even growth in hard times. Their views are drawn from interviews and written comments and combine the perspectives of young companies and old, public and private, in widely different businesses with sales ranging from the millions to tens of billions. But their general advice is surprisingly uniform. Keep expanding globally. Raise productivity. Focus on higher margin business.

A decade ago a lot of American companies were nervous about globalization and saw it only as a threat. The big lesson learned through the recent recession is that globalization in some form is necessary for survival. “If you rely on one country, the future goes as that country goes,” notes Joseph Pregont, CEO and president of Prent Corp., a privately held packaging thermoformer in Janesville, Wis., serving electronics, consumer products and medical customers. “We’re a miniature global company,” Pregont says with about half of sales from international plants in China, Denmark, and Malaysia. Last year Prent opened another foreign plant in Costa Rica.

“Slowdowns are often the right time for investments for those who can,” notes Serge Rogasik, V.P. for plastic additives in North America for BASF. BASF Group, headquartered in Ludwigshafen, Germany, a maker of pigments, antioxidants and light stabilizers for plastics, bought Swiss specialty chemical maker Ciba AG in 2009 at the start of the recession, and since then has invested in two new antioxidant plants in Bahrain and Singapore to support plastics growth. But “there are plenty of ways you can improve productivity and focus on higher margins without major investment,” BASF’s Rogasik adds.

In another recent downstream buyout PolyOne Corp. in Avon Lake, Ohio, is acquiring Spartech Corp. in St. Louis, Mo., a maker of specialty compounds, sheet and barrier packaging. The deal, which is expected to close in Q1, will bring PolyOne some specialty compounds for aerospace and security markets that it didn’t have before. Spartech can ride on PolyOne’s international sales presence to distribute Spartech products globally. And PolyOne hopes to apply operating efficiencies like its Six Sigma to Spartech production.

EXPAND SALES GLOBALLY

Prent malaysia

When thermoformer Prent expanded overseas with plants like this one in Malaysia, domestic employment grew because Prent builds its own thermoforming machinery in-house in the U.S. Prent’s U.S. employment actually grew 20% in the past four years supporting growth overseas.

Moving production offshore doesn’t necessarily hurt domestic employment either. When Prent set up its first overseas forming plant in Malaysia in 1998, Pregont explained to employees “that by moving thermoforming manufacturing overseas, we would actually create jobs at home, and we have.” The reason is that Prent builds its own in-line thermoforming machinery and automation in a separate machine building operation in Janesville, not just its molds. In-house machine building to support overseas expansion increased Prent’s domestic employment 20% over the past four years.

Machine builders sometime keep all or part of their manufacturing in the U.S. to protect proprietary technologies, and expand globally in sales. But U.S. manufacturing means high cost labor. Maguire Products Inc., a maker of feeders, blenders and dryers for extrusion in Aston, Pa., does all its manufacturing in eastern Pennsylvania and exports 50% of sales. In 2009 at the start of the recession, Maguire cut its workforce 15%, lowered remaining salaries for two months, and gave Fridays off. But cost cutting alone isn’t typically enough. At the same time, Maguire also shifted its focus to high-end new products and away from incremental growth in low margin products.

One such high-end new product was a custom blender with special bridge breakers to feed wood flour for plastic lumber, which Maguire had finished developing in 2008. Maguire realized that the same device could also feed bulk powders like calcium chloride, an extender in blown film and extrusion blow molded bottles. “We standardized it as the MaxiBatch line of blenders with five dosing devices for powder or flake or poorly flowing regrind and for liquid color or additives,” explains Pat Smith, V.P. of sales and marketing at Maguire. “That is a specialty item for other manufacturers.” Previously calcium chloride could only be fed in pellet form or using gravimetric powder feeders, which also cost three times more than MaxiBatch (about $100,000 vs. $35,000).

Maguire blenders

At the start of the recession Maguire Products standardized an unusual blender for bulk powders and filled warehouses in the U.K and Singapore with 100s of them, giving Maguire shorter lead times than European manufacturers, who custom build their powder blenders.

Maguire filled its warehouses in the U.K. and Singapore with the new blenders. “We have over 100 blenders in stock at any time. We have shorter lead time in Europe than European manufacturers do because they choose to build to order. We keep the pipeline full,” Maguire’s Smith explains. “We can absorb the carrying cost because we fill more orders than they do. It’s a huge competitive advantage.” Maguire continues to invest in high-end products like a new generation vacuum batch dryer, now in beta test sites, which will be introduced in 2013.

Sometimes you have to tweak your business model. Conair Group in Cranberry Township, Pa., a maker of auxiliary equipment including dryers, blenders, feeders, granulators, and downstream extrusion equipment, has been global since the 1970s with overseas sales, service and manufacturing in Mexico, Taiwan, Singapore, and China—all wholly owned, and most recently India. Conair president Larry Doyle is credited with having set up the Indian operation in 2007–Conair’s only overseas site that isn’t wholly owned–as a joint venture with NuVu Engineers, an established manufacturer of auxiliary equipment. “India was a unique situation,” Conair’s Doyle explains. “It is a natural partnership and a very successful one.” NuVu Conair has grown so rapidly despite the weak global economy that by 2010 it announced construction of a new manufacturing plant.

Conair Michigan Plant

In 2011, Conair added this 50,000 sq ft plant in Michigan to meet increased demand for high output downstream equipment for profile and tubing. The new equipment was developed by a specialized sales team focused on the needs of profile and tubing processors.

Another company that has seen foreign joint ventures grow gangbusters is Visteon Corp. in Van Buren Township, Mich., which makes automotive climate control, electronics and interior components, including plastics. Visteon’s 50% owned Yanfeng Visteon Automotive Trim Co. joint venture in Shanghai, China, with SAIC Motor Corp. (formerly Shanghai Automotive Industry Corp.) together with Visteon’s 70% owned Halla Climate Control Corp. joint venture in Seoul, Korea, which makes car climate systems, represent about 60% of Visteon’s revenue. Both joint ventures are growing much more rapidly than Visteon proper. Visteon now plans to sell its own climate control business to the Halla joint venture, which will make Halla’s climate business No. 2 in the world.

Yanfeng Visteon’s sales grow 28% a year, so Visteon president and CEO Tim Leuliette recently told a Barclays’ Global Automotive conference in New York that he expects Yanfeng could be bigger than Visteon next year. In an interesting twist on globalization, Yanfeng also intends to globalize its own interior car parts production. “No matter how good they are, regional players ultimately need to be global too,” Visteon’s Leuliette explains. “Interiors, instrument panels, seating, and other parts are over 70% of Yanfeng’s business. European car makers who use Yanfeng in China now want to use Yanfeng globally for other interiors too.”

RAISE PRODUCTIVITY

That means everyone–sales, manufacturing, and R&D. Communicating with global sales offices means starting the day earlier. “Your sales team has to be more 24/7 focused,” says Peter Cloeren, CEO of Cloeren Inc., a family-owned builder of flat extrusion dies in Orange, Texas, which manufactures all dies in the U.S. and exports 65%-70% of them. CEO Cloeren says he now starts work at 5:00 a.m. instead of 6:00, so he “can catch the Europeans in the morning and the Asians in the evening.”

Because Cloeren manufactures in the U.S., which is a high cost environment, manufacturing also had to get more efficient. Cloeren cut about 20% of employees after 2009, and at the same time invested substantially in new equipment to increase manufacturing productivity. “We’ve invested about $5 million in the last 12 months in new machine tools, which for a company of our size is a lot of money,” CEO Cloeren says of the stomach-knotting decision. “We bit the bullet, and we’re charging ahead.” The company is building a 10,000 square foot extension onto one of two die-building plants to house the new machine tools.

Sales people have to focus earlier and better on customer needs. Conair reorganized some of its sales force just before the recession, creating a new PET packaging sales team to understand the needs of PET film and sheet producers and get higher yields. Conair had previously dedicated sales teams to downstream extrusion of profile and tubing and to thermoforming. “There was certainly a downturn in 2009,” says Conair’s Doyle. “But Q1 and Q2 of 2010 were already better, and Q3 was strong enough to make new investments.”  By 2011 Conair had bought a 50,000 square foot plant in Pinconning, Mich., to meet increased demand for high-output cooling tanks, water baths, cutters and winders for pipe, profiles and medical tubing, developed with the sales team for profiles and tubing.

DuPont Zytel Plus

DuPont rapidly commercialized innovations like Zytel Plus in 2010, a new family of high heat nylons for use in new hotter, higher efficiency engines. General Motors used Zytel just 90 days after it was introduced to mold this Ecotec engine part for the Cadillac CTS.

R&D efforts also have to be targeted. “Be sure your R&D people are working on things that are meaningful,” cautions Diane Gulyas, president of performance polymers at plastics and chemical producer DuPont in Wilmington, Dela. Gulyas, who came up through 35 years at DuPont from field sales rep to lead the polymers business, became president in late 2009 just as the recession hit. As president, Gulyas pushed for innovations like the rapid commercializing of Zytel Plus in 2010, which won the “Most Innovative Use of Plastics” award from the SPE Automotive Division that year.

Zytel Plus, a new family of nylon resins that can withstand higher temperatures for longer time periods, was developed in record time in response to an urgent customer need. As car engines got smaller and more efficient, they were getting too hot for existing nylons. “Zytel Plus gave us 30-40 degrees F hotter surface temperatures. They were the fastest development we have ever done, between 9 and 12 months,” Gulyas recalls. New automotive materials typically take two to three years to commercialize. (BASF, for example, developed high-temperature-resistant Ultramid Endure for the same market, but had the first production application two years later in 2012.) Zytel Plus succeeded because DuPont R&D was put to work very early on a new customer problem.

DuPont Video Conference

In the past 18 months DuPont set up a network of nine Innovation Centers around the world with video conferencing and CAD/CAM seats to give customers direct access to any of 9500 DuPont scientists and engineers to meet customer needs faster.

Rapid commercialization of what customers need is also the goal behind DuPont’s new network of Innovation Centers around the world. There are nine so far built in the past 18 months in Japan, Korea, Taiwan, Thailand, India, Mexico, Brazil, the U.S., and Russia, all with video conferencing and CAD CAM seats to connect customers in those locations with some 9500 DuPont scientists and engineers anywhere in the world. Innovation Centers in Switzerland and Turkey will open in 2013, and an R&D and automotive center in China will be converted to an Innovation Center.

Focusing on aftermarket customer service is also an effective strategy in a slow economy, according to Husky Injection Molding Systems Ltd. in Bolton, Ont., which supplies injection molding equipment and services for beverage and food packaging, medical, and consumer electronics markets. Husky’s V.P. of marketing Jeff MacDonald notes examples like light weighting conversions and process and productivity monitoring software.

FOCUS ON HIGHER MARGIN PRODUCTS

In a slow economy concentrating resources onto higher margin business is important. Before the recession Nypro Inc., a contract injection molder in Clinton, Mass., had shifted its customer focus from three areas (consumer electronics, medical devices, and packaging) back to primarily medical devices and packaging, de-emphasizing wireless electronics. “They were becoming difficult for a contract manufacturer,” explains Nypro spokesman Al Cotton. “Customers were changing specs very fast, so it was costly for us.” That decision proved prescient. When consumer electronics manufacturing in Asia plummeted after 2009, Nypro wasn’t as exposed as it might have been.

Nypro’s globalization—41 locations in 14 countries, most in place for over 10 years—has been a boon for its medical device business. “We can do almost all medical devices where they’re being used,” Nypro’s Cotton explains. “That’s a big advantage in the medical business recently.” Nypro has also continued to invest in manufacturing for healthcare markets domestically, building two new clean rooms in 2012, one in North Carolina, where a customer got a state economic development loan, and one on its own in Clinton, where Nypro already had five clean rooms. The new one has higher output.

Sometimes a U.S. company becomes part of a foreign company’s global expansion and new opportunities open up. Before the recent recession Farrel Corp. in Ansonia, Conn., a builder of continuous mixers for plastics and Banbury batch mixers for rubber had neglected the continuous mixer side of its business and historically focused on the batch mixers. In 2009, Farrel was acquired by a German competitor, Harburg-Freudenberger Maschinenbau GmbH (formerly Thyssenkrupp Elastomertechnik GmbH), a unit of Possehl & Co. in Germany, which created a new HF Mixing Group and made separate business units out of Farrel’s batch rubber mixers and continuous plastic mixers. The batch mixer business unit moved from Connecticut to Farrel’s Rochdale, U.K. plant, which now concentrates exclusively on tangential batch mixers.

Farrel batch mixing

When Farrel was bought by a German competitor at the start of the recession, the new owner moved Farrel’s batch mixing business to the U.K., so Farrel could concentrate on continuous mixing and added in a new process lab in Connecticut for customer trials. Sales have grown ahead of budget.

Farrel in Connecticut was given worldwide responsibility for developing, building and selling continuous mixing machinery in the HF Mixing group, including the continuous mixers from Pomini Rubber & Plastics Srl in Castellanza, Italy (also a unit of Possehl). Despite the recession, Farrel’s new owner also invested in a spanking new process lab for customer trials in Connecticut. The lab opened in 2012 with all the usual test and analytical equipment plus “a new 550 kg/hour compounder for customer trials. The semi-works size is large for a lab, but allows accurate scale up to any production size,” says Stephen Peterson, V.P. and business unit director for the continuous mixing part of HF. “We have customer trials and development work every week now because we have the tools.” The result? “Order income is great now,” Farrel’s Peterson says. “We’re going to exceed our budget, and we’re going to hire new engineers.”

Not all investments bear fruit that fast. Nor are we out of economic uncertainty by any means. Both DuPont and Dow Chemical Co., Midland, Mich., for example, in their latest Q3 earnings reports for 2012 announced restructuring. DuPont’s Q3 report announced the elimination of about 1500 jobs globally in the next 1-1.5 years as part of its plan to divest the Performance Coatings business. Dow’s chairman and CEO Andrew Liveris told analysts that Dow would close nearly 20 “non-core” manufacturing sites and reduce capital spending. “Simply put, we have to… stop future growth projects that are no longer affordable in this environment.” Dow is not, however, stopping all growth projects. It continues to invest in differentiated, high margin products like the expansion of its Nordel elastomers and a plant in Texas for a new process to make propylene monomer based on shale gas feedstock.

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New Technologies in Stretching and Touching

By Jan H. Schut

New technologies appearing at the 2013 SPE International Polyolefins Conference February 24-27 in Houston (www.spe-stx.org/conference.php), include a developmental 77-nanolayer polyethylene shrink film with an extremely high stretch ratio and the first full conference session devoted to the emerging science of haptics in product design.

The unusual shrink film, developed by BBS Corp. in Spartanburg, S.C. (hschirmer@att.net), achieves high stretch ratios of seven times in both machine and transverse directions (7 x 7), where the normal stretch ratio for shrink film is 5 x 5. “Seven-by-seven is something to crow about,” says Henry Schirmer, principal of BBS, who presents the new film in “Nano-Layer Structural Advances in Shrink Films,” co-authored  by Jean-Francois Glez, R&D and product manager for the packaging division at Bollore S.A. (www.bollorefilms.com) in Quimper, France. Bollore, which makes biaxially oriented shrink films and thin capacitor films, worked with BBS for a year on the nanolayer shrink film.

Schirmer has given papers at Polyolefins conferences for over ten years on previous test work with his micro layer blown film die, called the Modular Disk Die, and on a Layer Sequence Repeater device that fits inside the die to form nanolayers. So that part of his development will be familiar. But this is his first report of stacking Layer Sequence Repeaters together to get to higher numbers of layers.

HOW 77 NANOLAYERS STACK UP

To reach 77 layers, Schirmer combined three Layer Sequence Repeaters inside a 6-inch die. The middle repeater forms 25 nanolayers; the other two form 26 layers, including a surface layer. The whole stack consists of 80 metal plates or disks, between which polymer flows to form successive layers onto the die mandrel. “Each and every nanolayer surface is formed separately between two metal surfaces with a mini-gap of 0.017 inches between them,” he explains.

This intensive contact of polymer with metal creates “parallel flow,” aligning polymer molecules without stretching them like parallel coiled springs, Schirmer postulates. When the film is biaxially oriented, the molecular springs uncoil, reaching the very high stretch ratios. Flow is slow through the die, and pressure is low–800 psi on the lab extruders, though at production rates, die pressure would be much higher (5000 psi). The relative thickness of layers is controlled by extrusion rate.

BBS’s nanolayering approach is quite different from creating nanolayers by splitting polymer flow and folding or stacking the multilayer flow onto itself to make more layers. That flat die technology was variously developed by Nordson EDI in Chippewa Falls, Wis. (www.extrusiondies.com); Dow Chemical Co., Midland, Mich. (www.dow.com); and Case Western Reserve University in Cleveland, Ohio (www.case.edu), and is used commercially to make cast films with anywhere from 25 to 800 nanolayers (see also this blog July 6, 2012).

BBS 77-nanolayer blown shrink films

BBS stacks three Layer Sequence Repeaters like this together to make developmental 77-nanolayer blown shrink films, alternating layers of two different PEs. The device forms individual nanolayers between metal plates with die gaps of only 0.017 inches.

BBS’s 77-nanolayer blown film alternates layers of two different polyethylenes, a departure for Schirmer, whose nanolayer R&D has mostly been with barrier resins like nylon, EVOH and COC (cyclic olefin copolymer). Bollore, however, had recently introduced a thin cross-linked shrink film (40-gauge) called BTTX110, which alternated metallocene PE and a different PE in a 7-layer structure, and Bollore wanted to test more layers to make even thinner, stronger shrink film.

Schirmer made test film with different structures of up to 77 nanolayers and shipped the rolls to Bollore in France, where the film was slit, partially cross-linked, and biaxially oriented on an R&D tenter stretching line with sequential MD/TD stretching. A 77-nanolayer film with two alternating PEs could be biaxially oriented 7 x 7 times to a thickness of 0.026 mil (26 gauge) or 6.5 micrometers with tensile strength of  23,057 psi, elongation at break of 79%, flex modulus of 300 MPa, and tear strength of 10.2 grams–all in TD. Good tear strength is the main advantage of the nanolayers, Bollore’s Glez notes. The film was also simultaneously stretched with the same test results, Glez adds.

Bollore biaxially stretched BBS's 77-nanolayer film

Bollore in France biaxially stretched BBS’s 77-nanolayer film on an R&D tentering line and achieved extremely high stretch ratios of 7 x 7 times—one of the highest ratios ever reported. Individual layers in the oriented film average only 8.6 nanometers thick.

BBS’s 77-layer film isn’t the first nanolayer blown shrink film, but it has the most layers and the highest stretch ratio. In 2009 the Cryovac division of Sealed Air in Duncan, S.C. (www.cryovac.com) commercialized 29-layer shrink film with 25 microlayers—which is still believed to be the most layers made commercially in blown film (see this blog June 17, 2011). Cryovac also describes achieving very high stretch ratios of 6 x 6 times.

BBS’s 77-nanolayer film also isn’t the most layers reported for blown film, at least not yet. In 2011, Dow introduced a nanolayer feed block technology, which creates a nanolayer melt and feeds it into a modified crosshead blown film die to make 114-layer blown film with 108 nanolayers (see this blog May 17, 2011). Schirmer, however, already plans more layers. He only stacked three Layer Sequence Repeaters together in the 6-inch die because that was the most that could physically fit. The repeater reduces the diameter of the 6-inch die to only 2 inches. Schirmer plans to scale up to a larger diameter die. “When that happens, it will double the number of potential layers,” he says.

PUTTING SCIENCE IN TOUCH

Scientific interest in haptics is growing. Many big companies today have research staffs studying perceptions of touch, which govern many purchasing decisions from car interiors to diapers. Yet there are still no test instruments or procedures to measure touch objectively. Color, sound, gloss, even odors can be accurately measured, but the sensation of touch is harder to understand and apply to product design, explains session organizer Cris Schwartz, an associate professor at Iowa State University in Ames (www.iastate.edu).

Schwartz has presented papers on haptics at Polylefins conferences before, but this time has assembled seven speakers, all doing active research in the new field. The seven speakers come from a wide range of perspectives, including that of a household products company, a business school, university research, and a resin company.

Schwartz simulates human finger tips with mechanical wands.

Schwartz from the University of Iowa simulates human finger tips with mechanical wands, objectively measuring and comparing the coefficient of friction generated off smooth surfaces and surfaces textured with parallel ridges. Smooth surfaces make more friction.

Session moderator Schwartz presents “Investigating the Haptics of Textured Polypropylene Using Friction Coefficient.” He uses mechanical wands with neoprene and silicone balls on the tips to measure the coefficient of friction off plain and textured surfaces. Human skin is 40 Shore A hardness, neoprene is 55, and silicone is 70, so they are similar in hardness. He compares COF data from smooth polypropylene panels and from panels with raised parallel ridges with different spacing by swiping human, neoprene and silicone “finger tips” in both parallel and perpendicular directions to the direction of the texture.  Results show that smooth surfaces produce the highest COF, as expected. A surprising result is that some textures produce the same COF when slid both with and across the direction of the texture.

Marc Masen, a mechanical engineer at the University of Twente in Enschede, the Netherlands (www.utwente.nl), reports on the contact mechanics of micro textures against human skin in “Friction Effects in Tactile Contacts.” His R&D began serendipitously when researchers at the university used lasers to cut micro textures into mold inserts and molded samples with micro textures. They discovered that some micro textures that were too small to see could make plastic feel soft to the touch.

University of Twente researchers discover micro textures in molded plastics reduce friction

Researchers at the University of Twente in Holland discovered that micro textures in molded plastic made the plastic feel soft by reducing friction with human skin. The idea is to reduce friction which causes bed sores in elderly patients in hospitals and nursing homes.

Vicky Polashock, a technical leader at Kimberly-Clark Corp. in Roswell, Ga. (www.kimberly-clark.com), shows how to apply the latest haptic research to product design in “Fundamentals of Haptic Processing of Everyday Textures.” Her research focuses on how neural receptors in finger tips are triggered by touching different surface textures, and how to use that information to predict sensory perception of objects. The skin in your finger tips and feet has four different types of neural receptors, which respond to sharp, rounded, smooth and rough surfaces and are well known. By increasing the frequency vibration of a stimulus to one type of receptor, she can dull sensitivity to that sensation, allowing her to study perception of different surfaces by the other neural receptors. She is trying to isolate how people interpret sensory information from each of the four types of receptors.

Dianne Pawluk, associate professor of Biomedical Engineering at Virginia Commonwealth University in Richmond (www.vcu.edu) describes “Haptic Perceptual Organization: Basic and Applied Research.” Her own research into haptics focuses on how to give better information through tactile markers to assist the blind and sight impaired. Her work aims at improving public policy on access requirements to help the sight impaired.

Pawluk researches perception of different shapes

Pawluk at Virginia Commonwealth University researches perceptions of different shapes to the touch, like roundness, sharp edges, and relief textures. Her research focuses on giving better tactile markers for public access areas to assist the blind and sight impaired.

Joann Peck, associate professor at the School of Business of the University of Wisconsin in Madison (www.wisc.edu), presents “Does Touch Matter? Insights from Haptic Research in Marketing,” analyzing what motivates shoppers to touch. Her research finds that people have very different psychological needs to touch objects before they buy. Roughly half of us have an acute need to touch things and are frustrated, for example, by online buying when they can’t touch, she explains. The other half doesn’t need to touch. She further finds that giving an enlarged image of a surface texture online for a product to show how it feels to the touch only satisfies people with a low need to touch in the first place, but still frustrates people with a high need to touch. In case you wondered why touching products is important, she explains that “if people can touch something, they’ll pay more for it.”

Roger Barker, director of the Textile Protection and Comfort Center in the College of Textiles at North Carolina State University in Raleigh (www.tx.ncsu.edu/tpacc), gives the science behind a variety of attempts at quantifying haptic responses in his “Overview of Modern Methods for Evaluating Tactile Response to Textile Materials.” Tanya Fry, Sensory Science Leader at Dow, presents “Making Sense of Polyolefin Product through Sensory Science.”

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Can Lowly Algae Save the Planet?

By Jan H. Schut

May be yes. May be no. They’re already grown on an industrial scale to make anti-aging pharmaceuticals and nutrients. But can algae also clean up industrial waste water and polluted fish farms? Convert CO2 emissions from utility and ethanol plants into oxygen? Make bioplastics? And replace fossil fuels? Those are tall orders for pond scum, but the emerging algae industry is targeting all of them—sometimes two or three at once.

BioProcess Algae LLC in Portsmouth, R.I. (www.bioprocessalgae.com), for example, just started up its first full size commercial algae plant on five acres next to Green Plains Renewable Energy Inc.’s bio ethanol plant in Shendandoah, Iowa (www.gpreinc.com). The algae farm eats CO2 emissions from the ethanol plant and produces animal nutrients. Algae carcasses after the nutrients are removed can potentially be used in bioplastics. BioProcess’ chief technology officer Toby Ahrens says they have been contacted by several research groups asking to sample algae residues for plastics.

BioProcess Algae’s new commercial algae farm next to Green Plains Renewable Energy’s ethanol plant in Iowa eats CO2 emissions from the ethanol plant and produces animal nutrients. Algae carcasses after the nutrients are removed can potentially be used as a filler in bioplastics

BioProcess Algae’s new commercial algae farm next to Green Plains Renewable Energy’s ethanol plant in Iowa eats CO2 emissions from the ethanol plant and produces animal nutrients. Algae carcasses after the nutrients are removed can potentially be used as a filler in bioplastics.

The Algae Biomass Organization in Denver (www.algaebiomass.org), a four-year-old trade group formed to promote industrial algae, says the rapidly growing industry is already $1.2 billion/year. But that’s actually the value in 2010 of pharmaceutical algae (carotenoids) alone. (Pharmaceutical powders with 5-10% active carotenoids can also cost $300 to $3000/kg, according to a recent paper by Herminia Rodrigues, professor of biochemistry at the University of Seville in Spain.) All the other industrial applications for algae–waste water cleanup, CO2 emission abatement, bio fuel and bioplastics–are in stages of R&D or early commercialization.

Algae are single- or multi-celled organisms that can grow in water either alone or in strings or colonies. They can be macro like seaweed or micro like slime. They can be photosynthetic getting energy from sunlight, breathing in CO2 and respiring oxygen, then at night reverse and breath in oxygen and out CO2. Algae can also be heterotrophic, getting energy from sugars and continually respiring CO2. Brown algae, like Phaeophyceae, are usually marine and are used to remove heavy metals from water. Green algae are usually in fresh water, like macro algae found in fish farms, or microalgae Chlorella and Spirulina, which are used to purify waste water and remove CO2. The ritzy carotenoid-producing algae used by the pharmaceutical industry can be yellow and bright orange. Cyanobacteria are photosynthetic bacteria, not algae, also being developed to produce biomonomers and abate CO2.

Algae use in bioplastics is in its infancy. Three companies have published or announced blending algae into thermoplastics. Cereplast Inc., a compounder of starch-based biopolymers in El Segundo, Calif. (www.cereplast.com) compounds post-industrial algae into thermoplastics. Algix LLC in Bogart, Ga. (www.algixllc.com), a spinoff in 2010 from the University of Georgia in Athens (www.uga.edu), is developing blends of unprocessed algae into thermoplastics under a global license (U.S. Pat. Applic. # 20100272940) from Kimberly-Clark Corp. (www.kimberly-clark.com) in Irving, Texas (see this blog posted Nov. 8, 2011).

CEREPLAST COMMERCIALIZES WORLD’S FIRST ALGAE PLASTIC

In September 2009 Cereplast announced that it had successfully blended algae into PP. Cereplast had just licensed patented technology for making bio-content degradable polymers (U.S. Pat. # 7608649) from the University of Arkasas in Fayetteville (www.uark.edu) and wanted to offer algae-content in degradable polymers. But Cereplast assumed that post-industrial algae wouldn’t be available in large enough quantities until algae biofuels became commercial. Instead Cereplast found postindustrial algae were already available.

Different kinds of algae have different starch, fat, protein and fiber content, but post-industrial algae, which consists of the carcasses or cell walls left over after oil or medicinal contents have been extracted, is largely lignin and cellulose and fairly consistent regardless of algae type. “We care more about the industrial process the algae comes from than about the kind of algae,” says Cereplast senior v.p. of R&D Kelvin Okamoto.

Cereplast first developed algae-content thermoplastic in 2010 and introduced it commercially this year as Biopropylene 109D with 20% post-industrial algae biomass in PP. Biopropylene 109D is designed for thin-walled injection molding with density of 0.94 g/cc, melt flow index of 24 g/10 min. at 190 C and flex modulus of 125 kpsi (see data sheet). The first commercial application is for luxury hair accessories injection molded in France for the Barrette Factory in Hollywood, Calif. (www.dominiqueduval.com), which promotes Cereplast’s algae plastic on its website. Algae add some desirable properties, especially soft haptics, a natural feel, and better grip for hair products, says Jane Gauthier, designer for the Barrette Factory.

Barette/Cereplast

The first commercial algae-thermoplastic products in the world are a line of luxury hair accessories injection molded in France for The Barrette Factory. They use a new grade of 20/80 algae/PP compounded by Cereplast and boast improved haptics and a natural feel.

Properties of Cereplast’s New Biopropylene 109D
Algae content, % 20
Density, g/cc 0.94
Tens. Strength @ max., psi 3,460
Tens. Elong. @ break, % 3.3
Tens. Modulus, kpsi 240
Flex. Modulus, kpsi 125
Flex. Strength, psi 3,630
Gardner Impact, in-lbf 20
MFI 190 C @ 2.16 kg 24 g/10 min
MFI 230 C @ 2.16 kg 78 g/10 min

In packaging algae they can add biodegradability. Cereplast has experimental grades with up to 50% algae content. Algae also add color, either green or brown, and unfortunately odor. Both depend on the type of algae and the industrial process it comes from, so Cereplast keeps algae from different post-industrial sources separate. “Algae smell like the ocean,” notes BioProcess’ Ahrens, “but they shouldn’t smell like the ocean at low tide.” Processing algae to remove nutrients or oil reduces the odor, but when a closed box of plastic pellets with algae content is opened, it still smells. Secondary processing, however, for example by injection molding, reduces the odor further, so that Barrette Factory’s Gauthier says odor isn’t an issue.

 

ALGIX IS SCALING UP BLENDS OF ALGAE WITH PP AND PBAT

Algix this year received a $100,000 grant from the University of Georgia and $500,000 of private capital to scale up production of algae-content bioplastics. Algix initially took dried algae cultivated from waste water cleanup from Ven Consulting LLC in Melbourne, Fla., and ground it with a hammer mill to a particle size of around 250 microns. The algae was then compounded into polypropylene at up to 50% loading and extruded into sheet at Interfacial Solutions LLC, a contract R&D company in River Falls, Wis. (www.interfacialsolutions.com). Algix’s director of R&D Ryan Hunt notes that about 500 microns was the thinnest sheet they could make. Hunt had been in communication with Dordan Manufacturing Co. in Woodstock, Ill. (www.dordan.com), which wanted to test the new algae/PP sheet, so Algix sent Dordan the test roll. Dordan formed it and showed algae/PP test samples at Pack Expo in Chicago in October.

Algix green microalgae compounds

Algix, a spinoff from the University of Georgia, is scaling up compounds of green microalgae with PP and the biopolymer PBAT. Target applications are for sheet for thermoforming and injection molding of containers for lawn and garden products.

Algix next tried jet milling the dried algae to finer particle size (10 microns) and compounded it into both PP and poly(butylene adipate-co-terephthalate). In January 2013 Algix plans to make a larger run of 2000 lb of dried algae, compounded into both PP and PBAT to sample to companies that want to develop applications with it. One potential application is for injection molded containers for lawn and garden products, Algix’s Hunt says, where odor won’t be an issue. For injection molding the particle size of the algae doesn’t have to be quite as small as for thin films for packaging, Hunt adds.

ALGAE CAN ALSO MAKE BIO-POLYMERS

Growing algae to make jet fuel and gasoline, the application the government likes to talk about the most, is probably the farthest from commercialization, though there are over 30 start-up companies in the U.S. alone working on it. The criticism leveled at algae biofuel technologies is that they consume way too much fresh water and energy for aeration to be environmentally sustainable. The advent of inexpensive shale gas in North America is also likely to slow algae biofuels. But some algae biofuel companies target making chemical intermediates like bio ethanol and lactic acid for biopolymers.

Algenol Biofuels Inc. in Bonita Springs, Fla. (www.algenolbiofuels.com), has selectively enhanced cyanobacteria (U.S. Pat. Applic. # 20100297736 and 20120142066), which live in salt water, eat CO2 from industrial waste, and give off ethanol and fresh water without killing the bacteria. This saves time and resources needed to grow new bacteria and the cost of separating ethanol. Algenol is building a farm of closed plastic reactor tubes in Lee County, Fla., hoping to produce ethanol for around $1/gallon. “We also would consider converting ethanol into ethylene,” says Algenol’s chairman and CEO Paul Woods.

Algenol Biofuels Cyanobacteria Incubators

Incubators for the ethanol producing (genetically engineered) cyanobacteria–a photosynthetic bacteria.

Inventure Chemical Inc. in Tacoma, Wash. and Tuscaloosa, Ala. (www.inventurechem.com), uses a catalytic reaction and esterification technology (U.S. Pat. Applic. # 20110162951) to convert algae to chemical intermediates like ethanol and also recovers starch and cellulose.

A new research group in Germany from the Institute for Synthetic Microbiology (www.synmikro.com), set up in 2010, with Philipps University in Marburg (www.uni-marburg.de) and Westfaelische Universitaet Muenster (www.uni-muenster.de), has come up with the first algal production of poly-3-hydroxybutyrate (PHB). Researchers injected the diatom Phaeodactylum tricornutum with three bacterial enzymes that together make PHB. After seven days, the algae accumulated granules of PHB up to 10.6% dry weight. That’s less far efficient than bacteria, which can yield 80wt% PHB, but with photosynthesis algae could be less expensive to grow.

Synmikro PHB from algae cells

A new research group in Germany at Synmikro has developed the first PHB from algae cells, which in seven days accumulated 10.6wt% PGA. That’s less efficient than bacteria, which can yield 80wt% PHB, but could be less expensive to grow because of photosynthesis.

Interesting high value polysaccharide polymers are also being extracted directly from specialized algae. Georgia Institute of Technology in Atlanta (www.gatech.edu) and Clemson University in Clemson, S.C. (www.clemson.edu) discovered a polysaccharide from brown marine algae that could allow greater energy storage in lithium ion batteries. The materials are being developed by Sila Nanotechnologies Inc. (www.silanano.com), a spinoff from Georgia Tech. Marine Polymer Technologies Inc. in Danvers, Mass. (www.marinepolymer.com) extracts chitin from brown algae, then extracts N-acetylglucoseamine monosaccharides from the chitin. It’s used to make dressings that can stop bleeding even from open wounds.

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Rumplestiltskin Wanted

By Jan H. Schut

Someone to spin straw into gold, or in this case lignin into plastic. Government money pours into public universities and research centers in places with forestry industries in Canada, Finland, Sweden, Germany, and the northern U.S.—including $120 million worth of recent grants from the U.S. Department of Agriculture for cellulosic biobuels and high value applications for lignin in plastics.

Lignin is the second largest natural biopolymer on the planet after cellulose, wood being roughly 15-35% lignin depending on species and the rest cellulose and hemicellulose.  One hundred billion lb/year of lignin is separated globally as a byproduct of wood pulping. Only 2% of that is sold commercially, however, for things like stabilizers in asphalt and dispersants in concrete and textile dyes; 98% is burned internally by pulp mills for energy. An infinitesimally small amount of the commercial 2% is used in plastic, mostly thermosets and adhesives.

Why so little? Lignin is a natural polyphenol, so it can be substituted for some phenolics in thermosetting formaldehyde resins and for some polyols in epoxies and polyurethanes. It’s inherently anti-fungal and improves U.V. resistance. But phenols can slow down reaction time, so typically only 10-15% can be added. Color is also an issue. Industrial lignins are relatively low purity and typically brown, though they can be light and can be bleached. Lignin can also be added to thermoplastic polyurethanes.

Adding it to other thermoplastics, however, is harder. It can only be done if you have thermoplastic lignin, and not much thermoplastic lignin is commercially available. Thermoplastic lignin must have a specific molecular weight, purity, solubility, and thermoplasticity. It can be made by “fractionation” of lignin into distinct molecular weight fractions, mostly by filtration, or by chemical modification, such as acetylation.  Isolation from pulping liquors can also be done for higher purity lignin. Otherwise lignin’s branched structure with methoxyl and aliphatic hydroxyl groups, plus chemical residues from pulping, make it unusable.

Only one company in the world has ever successfully commercialized lignin-based thermoplastic compounds—Tecnaro GmbH, Ilsfeld, Germany (www.tecnaro.de), a spinoff from the Fraunhofer Institute for Chemical Technology in Pfinztal, Germany (www.ict.fraunhofer.de) in 1998. Tecnaro developed a patented process (U.S. Pat. # 6509397) for compounding lignin with natural fibers into 100% biobased thermoplastic resins. Its Arboform resins combine lignin with oils, waxes, natural fibers and other biobased additives to increase impact strength and are mainly for injection molding, but also for extrusion, calendaring, thermoforming and compression molding. Its Arboblend resins combine biopolymers like lignin, starch, biopolyesters, cellulose, biopolyamide and biopolyolefins and are for film extrusion.

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Only one company in the world has successfully commercialized lignin-based thermoplastics, Tecnaro in Germany, which blends lignin with other biomaterials to make 100% biobased grades, meeting stringent requirements for high end applications like these loudspeakers.

NEW LIGNIN-CONTENT PLASTICS

Recently, however, three new lignin-content plastic technologies have appeared. Two are thermoplastic; one is thermoset. Two are going commercial, which is astonishing given the difficulties and limited supply of usable lignin. Oak Ridge National Laboratory in Oak Ridge, Tenn. (www.ornl.gov) presented a new lignin-content elastomer technology for the first time at the Society of Plastics Engineers’ ANTEC Conference last May. Oak Ridge’s technology creates high molecular weight lignin, then blends it with functionalized PBD to make thermoplastic elastomer copolymers. Oak Ridge staff researcher Amit Naskar says the patent-pending technology creates a two-phase morphology over a range of blends with 10%-50% lignin.

In Oak Ridge’s process lignin with a weight average molecular weight of about 1000 g/mol is washed in solvents to remove low molecular weight fractions, yielding lignin with about 10,000 g/mol, which is cross-linked with formaldehyde to reach about 30,000 g/mol. This high molecular weight lignin is compounded with soft oligomers to make melt-processable, two-phase copolymers. The soft segments are dicarboxy-terminated, so they react with natural hydroxyl groups on the lignin to improve impact strength. Cross-linked lignin hard segments, which have no detectible Tg, are bridged with low Tg soft segments, making the copolymers melt recyclable. The technology is available for license and could also combine high molecular weight lignin with biopolyesters to make 100% biobased resins.

Another new flexible lignin-content thermoplastic is being developed by a start up venture CycleWood Solutions Inc. in Fayetteville, Ark. (www.cyclewood.com), licensed from the University of Minnesota, St. Paul (www.umn.edu). CycleWood modifies the lignin differently from the method in the patent (U.S. Pat. # 6172204), “which wasn’t commercially feasible,” COO Kevin Oden explains. CycleWood then blends the modified lignin with an undisclosed thermoplastic to make blown film for compostable bags. Scale up work has gone on for a year with the polymer program at the University of Dayton (www.udayton.edu) and made around 300 lb of lignin-content plastic, which has been tested on a lab scale for both cast and blown film. The film is paper bag color and matte finish. It will have to be slightly heavier gauge than conventional HDPE bag film, but will still be less expensive than commercially available compostable materials, Cyclewood’s Oden says. CycleWood, which has won numerous awards for its business plan including an Edison Award, was created by four students in an entrepreneurship class in an MBA program at the University of Arkansas, Fayetteville (www.uark.edu), who found the University of Minnesota technology by searching online. Three of the four partners are also engineers.

Another interesting new development is a lignin-content thermoset.  Enerlab 2000 Inc. in St.-Mathieu de Beloeil, Que. (www.enerlab.ca), a maker of PU and PIR foams, has developed lignin-content polyisocyanurate foam and is commercializing it for insulation boards, believed to be a first. Enerlab started the R&D in 2010 as part of a program with the National Research Council of Canada (www.nrc-cnrc.gc.ca). The goal was initially to substitute 10-20% of polyol with lignin, but Enerlab found it could go higher without hurting properties. Enerlab demonstrated the feasibility of making 22% lignin-content foam and is building the industrial process on a pilot scale now. The company expects to commercialize the first renewable-content PIR foam boards early in 2013, says Enerlab president Armand Langlois. Enerlab is extending its technology next to structural insulated panels and spray foam.

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Enerlab 2000 tested lignins from different pulping processes and different tree species to develop the first polyisocyanurate foam boards with renewable content. Boards with 22% lignin content will be commercialized next year. Insulated panels and spray foams will come next.

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LIGNINS ARE COMPLICATED

Different pulping processes produce different lignin types, some water soluble, some not, with different chemical residues. Both water soluble and insoluble lignins can be fractionated for consistent molecular weight and modified for both thermosets and thermoplastics. But water insoluble lignin is easier to use in plastics and more weather-resistant than water soluble lignin. The two biggest wood pulping processes are sulfate (Kraft) and sulfite. Sulfate/Kraft process lignin isn’t water soluble and is mostly burned by pulping mills for energy, except a small amount that is sulfonated for water solubility and sold as emulsifiers and surfactants.  Sulphite lignins, made in both acid and alkaline pulping processes, are water soluble and often not burned by mills, but sold as emulsifiers and surfactants.

Two newer pulping processes make high purity lignin which is more promising for plastics. A soda pulping process for straw in India, developed by GreenValue SA in Orbe, Switzerland (www.greenvalue-sa.com), makes high purity lignin that is water insoluble and nearly thermoplastic. Reportedly it can be modified for softening temperatures down to about 130 C.  GreenValue is the only large scale commercial source for high purity lignin and sells its products for resins for high-pressure laminates and to several wood-panel mills in India for low-formaldehyde adhesives. GreenValue also sells lignin products for thermoplastics.

Pure Lignin Environmental Technology Ltd. in Kelowna, B.C. in Canada, a 12-year-old company with a patented (U.S. Pat. # 7396434) dilute acid process to separate cellulosics from lignin, also can produce thermoplastic lignins, both water-soluble and insoluble, for use as a filler in plastics, including PP and PE. Pure Lignin says it has sampled numerous test applications and has just licensed its lignin for use at 10-20% in PP. Pure Lignin says 20% lignin in PP and PE improved tensile modulus and flexural modulus by over three times. Its lignin is based on biomass from any vegetation, not just wood.

The great hope for thermoplastic lignin, however, is the so called “organosolv” biorefining process for biofuel. A half dozen biofuel technologies are at the pilot plant stage, but not commercial. The original organosolv biofuel process was developed by a GE Venture Capital company in the ‘80s, called Biological Energy Corp., for alcohol-based wood biorefining. GE intended to convert cellulose into biofuel and sell thermoplastic lignin as a plastic additive, but when oil prices fell, GE backed out and sold the venture to Repap Enterprises Inc., a large Canadian paper company.Image

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Lignin from paper pulping is typically brown and has a complex structure with methoxyl and aliphatic hydroxyl groups. It can’t be used in plastic without modifying its molecular weight.
Photo: Oak Ridge National Laboratory; Schematic: National Research Council of Canada

Repap wanted the environmentally friendly pulping process, called it Alcell (for alcohol cellulose), and invested $60 million in a demonstration pulping mill. Repap also developed the first lignin-content thermoplastic, putting its patented lignin (U.S. Pat. # 5321065) in powder form (1-5 microns) into LDPE. Repap compounded masterbatches with up to 75% lignin and blew compostable mulch film with 13% lignin. The film was blown in France and the U.S. for sampling. But Repap was heavily in debt for overbuilding paper capacity ahead of a recession and was taken over by a hedge fund and the company broken up.

The Alcell biofuel technology passed to the Canadian government and then to investors who formed Lignol Innovations Ltd., Burnaby, B.C. in Canada (www.lignol.ca). Lignol still has the original GE pilot line and in 2009 built a larger demo plant for high-purity thermoplastic lignin, which Lignol says it has supplied for PP and thermoplastic PU. Because many of the old GE and Repap patents have expired, Lignol requires a “material transfer agreement” with customers to protect its technology.

Historically, the first commercial lignin plastic goes back further than Repap. It was probably a thermosetting adhesive invented by a father/son team in Canada in the 1950s. George Tomlinson Sr. found a way to cook and isolate lignin from sulfonate/alkali paper pulping, then with son George Jr. used the lignin to replace phenolic in thermosetting formaldehyde adhesives. The Tomlinson technology was commercialized by Arborite Co. in Montreal, now a unit of ITW (www.arborite.com), which used lignin in adhesive to make laminated wood kitchen counters.

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