Milestones of the Organic Metal Polyaniline Science & Technology

http://www.bernhard-wessling.com/pani/welcome.html http://www.bernhard-wessling.com/pani/company/milestones_highlights.html Milestones and Highlights of the Organic Nanometal (Polyaniline) Science & Technology Research and Development 1978 B. Wessling started as a fresh PhD chemist in a small company ("SAPCO") and read first articles about conductive polymers, one of them the article describing the discovery of the first highly conducting organic polymer, polyacetylene, written by the later Nobel prize winners (2000) A. Heeger, A. MacDiarmid, H. Shirakawa. Wessling began work in compounding thermoplastic polymers, the first step into the dispersion field 1978 only on and off thinking about how to enter the conductive polymer research while introducing the first thermoplastic compounds produced by the newly developed dispersion method; already roughly conceived a 1981 hypothesis for later conductive polymer research: how to overcome the insolubility of polyacetylene – by compounding? by dispersing? Already at that time, the literature showed the paradigm under which the scientific community was working: they wanted to make the conductive polymers soluble and moldable (cf 1996 publication about insolubility of conductive polymers) 1981 changed to Zipperling Kessler (Ahrensburg) in a position as Director R&D, began development of many new thermoplastic dispersion processes and products, e.g. antistatic record molding compounds, an invention (priority date Dec 31st, 1983) which came far too late from the viewpoint of the old generation music lovers who used to listen to pressed vinyl records; at that time, the company is in very bad shape; had fired 2/3 of the employees, less than 50 left, and only one product group – the outdated record molding compounds (PVAc-PVC blends), no equity left, only debt; Wessling introduced many new products and changed the strategy to become a specialist: "Make your innovation to be our problem", was the marketing philosophy. 1982 started active research on polyacetylene, discovered the globular morphology of polyacetylene which was 1984 published in June in German in "Makromolekulare Chemie", a pdf is available here 1984 June 15, priority date (German priority patent application) for the first groundbreaking conductive polymer dispersion patent soon after, another groundbreaking patent was filed which contained the first elements of a deeper understanding about the principles by which conductivity in heterogeneous (polymer) systems is emerging: 1984 Nov 7 priority date (German priority patent application): "conductive pathways" have been developed and described. This principle was widely used by Zipperling Kessler in their carbon-black filled thermoplastic antistatic compounds products line which was a leading technology in the market; it required Wessling to invest deep research until year 1987 when he succeeded to uncover the secrets of how conductive particles dispersed in a (thermoplastic) polymer will cause conductivity when present in a concentration above a certain well-defined critical concentration (published 1991, available aspdf): it is not a percolation phenomenon, but a phase transition from dispersed to flocculated submicroscopic (nanoscopic) morphologies (as it took more about 3 years until finally a publication was accepted, several journals had refused to publish the article, Wessling decided to document the priority of this important discovery by filing a British Patent Application: GB-OS 2 214 5l I date of filing: Jan. 23. 1989. date of publication: Sept. 6. 1989). 1984 another attempt to overcome the serious limitations of how to process conductive polymers in industrial scale, how to get various forms (shapes) of products was also filed in 1984 (June 14), this technology subproject was later discontinued when it didn't show any further promising improvements. 1986 (July) biannual International conference on Synthetic Metals (ICSM) was held in Kyoto; B. Wessling gave an oral presentation and presented his concept for how to process conductive polymers for the first time to a broad audience ("Post-polymerization processing of conductive polymers: A way of converting conductive polymers to conductive materials?", in: Synthetic Metals 15 (1986) S. 183 – 193); a funny side note: as the Organizing Committee and the International Scientific Advisory Committee did not know Wessling at all, and had no clue about what his abstract was talking about, it took Wessling a long time to convince them he should be accepted for an oral presentation; but as the program already was full, he was placed at the very end of the conference, just before the official closing of the conference; more than 1,000 people attended this plenary lecture – but (except 1: Ron Elsenbaumer) probably none of them caught the idea; anyway, this lecture was the beginning of a long „Wessling in ICSM history“ which was full of controversy and of only very slowly increasing degree of acceptance. The controversy was about Wessling's growing doubts that conductive polymers may not be soluble; it took him 10 years until he was able to show (1996) that conductive polymers are intrinsically insoluble and unmoldable 1984 during these 12 years, Wessling and his growing research team at Zipperling made continuous progress and filed a lot ofpatents; all kinds of different conductive polymers were studied and evaluated for usefulness under industrial 1996 conditions, finally decided to focus on polyaniline; also many scientific papers were published (a publication list from 1986 – 2003 on the web) (another publication list from between 1993 and 2001 on the web) 1984 during this time, Zipperling actively cooperated with Americhem, Inc., Cuyahoga Falls, Akron, Ohio (US) 1996 1985 Wessling got appointed as CEO of Zipperling Kessler (continued to be R+D Director), later he bought a significant amount of shares when several shareholders wanted to leave the company 1987 (priority date September 4) groundbreaking patent describing a new process which allows to produce dispersible conductive polymer powders; later the focus was more and more on polyaniline, finally its most stable p-toluene sulfonate compound 1989 Zipperling entered into a cooperation agreement (joint research and development agreement) with Allied Signal, who at that time had the biggest conductive polymer research group in the whole world; later, Zipperling granted a patent license to Allied Signal 1993 (priority date May 17) another one of the key patents was filed describing a completely new first dispersion step (which later was discovered to cause the insulator-to-metal transition); 1990 research cooperation with the group of Prof. Nimtz (Univ Cologne) begins, exciting results are published in the following years showing that the primary particles of Ormecon's polyaniline contain a nanoscopic metallic core which later (1996 – 1998) lead to the discovery of the „insulator-to-metal-transition“ 1991 a first thermoplastic polymer blend was developed which the 3 partners (Zipperling, Americhem, AlliedSignal) tried to market as EMI shielding compound; this market strategy was later abandoned because of lack of demand 1991 first part of a non-equilibrium thermodynamical theory of heterogeneous polymer systems completed and published by Wessling; it takes him until 1995 to widen and deepen the understanding of the non-equilibrium character of polymer blendsand generally „dispersions“ 1991 Wessling describes and comments the critical situation in the world-wide conductive polymer research arena, his "Talking Point" was published in "Advanced Materials"; he was also citing a small workshop on Materials Science of Conductive Polymers he and Ron Elsenbaumer had organized bringing together 12 key players of the ICSM arena, including the later 2 Nobel prize winners MacDiarmid and Heeger, as well as (under others) Epstein, Geniès and Nimtz; Wessling's presentation was published as a full paper 1992 B. Wessling got appointed as a member of the International Advisory Committee of the ICSM; since then, he was the only industrial member of this biannual global conference scientific advisory committee, any other member was a professor at a university 1993 another key breakthrough was the discovery of the passivation effect of polyaniline (more information)(article in Adv Mater) which lead to the development of a powerful corrosion protection process and products therefore (patent application June 25, 1993); 1996 the passivation mechanism was revealed 1995 based on the fundamental polymerisation and dispersion discoveries and developments, another groundbreaking patent was filed (priority Nov 29, 1995): this patent so far was the commercially most important one (would have been impossible without the previous ones which had built the fundament); it finally lead to the Immersion Tin surface finish process ORMECON CSN which is a most successful product leading the ImSn PCB surface finish technology and market 1995 key scientific breakthrough: part 2 of the non-equilibrium thermodynamical theory of heterogeneous polymer systems and dispersions was published 1995/ Zipperling's CEO B. Wessling decides to separate the (Zipperling) compounding activities from the polyaniline 1996 related activities and forms Ormecon Chemie GmbH & Co KG as a 100% subsidiary of Zipperling Kessler, starting with 7 ex-Zipperling employees; B. Wessling also to act as Ormecon CEO; reason for this decision: compounds and polymer blends using Polyaniline did not seem to become successful, while PCB surface finish and corrosion protection as well as other dispersions offered more market chances; because not only the markets, but also the production technologies used in the meantime had developed to be far away from what Zipperling was using for compounding, the separation was necessary (also for preventing that the compounding business became diluted and weakened because of capital needs for the polyaniline products development and market introduction) the original strategy was to focus on the corrosion protection products, Wessling assumed the market entrance barrier to be low; for the PCB market he correctly assumed a high market entrance barrier due to customers would not take new processes from unknown suppliers and surface finishes mostly rquire release by OEMs / end customers before a PCB manufacturer could use them (therefore, it was Wessling's strategy to partner up with established big chemicals suppliers); first it seems to be a correct assessment, as market entrance progress with CORRPASSIV was dynamic and the interest by in total 4 chemicals suppliers to work with Ormecon for the introduction of the new CSN process was also high; but one after the other cooperation failed during Ormecon already succeeded to get first demonstration customers in Europe, while on the other side, only a few commercial orders for singular unique corrosion protection projects had been sold; therefore, mid of 1999, the strategy was changed and the major focus was on the PCB market without reducing the effort for corrosion protection products to Zero; this strategy change was successful 1996 July 3rd: Zipperling Kessler sells its compounding business with all assets to Clariant; at this time, Zipperling has > 300 employees and is highly profitable with an equity/debt relation of 45/55; Zipperling, since then acts as a pure holding company, holding 100% of the Ormecon shares 1996 In a plenary lecture on ICSM 1996, Wessling presents an overview about the recent basic scientific discoveries and the commercial applications now possible using Ormecon's polyaniline dispersions ("Scientific and Commercial Breakthrough"). 1997 (priority date July 25) another key discovery was made and developed into a patentable process: polyaniline can form distinct complexes with certain metals, especially Fe, Cu and Zn; later, this invention proved to be the key principle of the Organic Metal's outstanding performance in corrosion protection and PCB (Cu areas) final finishing 1997 B. Wessling contributes a chapter to H. S. Nalwa's (ed.) "Handbook of Conductive Molecules and Polymers" with a subchapter about "Rheological phenomena and Structure Formation in Multiphase Polymer Systems" 1998 in a research cooperation with the group of Prof. Nimtz (Univ Cologne) and a group in India, Wessling finally concludes that during a first key dispersion step, Ormecon's polyaniline changes its character from being on the insulator side to the metallic side of the insulator to metal transition; oral presentation at the ICSM 1998; 12.-18. July 1998, Montpellier/ France: "Polyaniline on the Metallic Side of the Insulator-to-Metal Transition due to Dispersion: The Basis for successful Nano-Technology and Industrial Applications of Organic Metals", full paper: Synth. Met. 102 (1999), p. 1396-1399 these and following publications had been the result of an intensive research work which was also partially done in cooperation with Prof. A. Kaiser in New Zealand, during which the metallic character became more and more obvious, better and better understood 1996 ICSM 1996: Wessling presented another step towards to final conclusion about the metallic character of the Organic Metal 1996 during the almost 13 years of Ormecon's company life, it grew from 7 to over 60 employees and introduced several products into the markets, the most successful one is ORMECON CSN, a final surface finish for printed circuit 2008 boards. Many more patents have been filed (see also patent system description here, status 1997) and scientific papers been published, partiallyalso after Ormecon was sold to Enthone in Sept 2008 (publication list)(more recent publications) some popular scientific articles promoting Ormecon technology: • about corrosion protection (in German) • Organic Metal technology (Chemistry in Britain) • introduction into the Organic Metal science (ACS Chemical Innovations) (original source) • ABC Science Online about corrosion protection 1996 another scientific breakthrough: Wessling succeeded to prove that conductive polymers can not be soluble; this was first presented at a symposium in Bayreuth (Germany). There are no publications (so far, 2013) showing any solid evidence that the facts and theoretical considerations shown and discussed in this paper are inappropriate, inconsistent or otherwise not correct; one can therefore be quite sure that conductive polymers are not soluble, and whatever other groups have published as "solutions" had in fact been dispersions 2000 it was later published as part of a broader article in the "Handbook of Nanostructured Materials and Nanotechnology" (H. Nalwa, ed; Academic Press), as chapter 10 "Conductive Polymers as Organic Nanometals", p 501 - 576 1998 (April) after AlliedSignal had sold its Polyaniline activities to Monsanto, the cooperation was first continued between Ormecon and Monsanto; however, soon after, Monsanto changed their strategy to completely focus onto agriculture and transferred all (former Allied Signal / Monsanto) polyaniline related patents to Ormecon 1998 the SEAM 1998 award was given to Bernhard Wessling for his pioneering contributions to science and technology of conductive polymers and to commercialising them. The presentation given at the conference where the SEAR award was presented was published in Synthetic Metals: "Dispersion as the link between basic research an commercialisation of Conductive Polymers", a paper which describes the key strategic role of "dispersion" in this area. 1998 first ORMECON CSN customers outside of Germany, in GB 1999 - ORMECON CSN became successfully introduced in Korea; continuous development (one of which the patent 2004 application for and immediate market introduction of a whisker reducing process) and process improvements result in more and more OEM approvals and steadily increasing market share 2000 ICSM 2000: Ormecon presents 6 papers; the organizers (Prof. Sariciftci and his group) and B. Wessling had initiated to sponsor an „Industrial Award“ for the most striking and most promising research presented on each ICSM; Wessling was the jury speaker, Prof. Heeger and others were part of the jury; Wessling's speech on the conference dinner announcing that the first Industrial Award was given to Bertram Batlogg and Hendrik Schoen; only much later, it became evident that Hendrik Schoen had published massive amounts of fake results (1 example showing "this article has been retracted") 2000 Covion (later part of Avecia which later became part of Merck KGaA) acquired a license from Zipperling for the use of polyaniline in OLEDs 2001 (February) a patent license was transferred to the Finnish Polyaniline producer Panipol whose products infringed Zipperling / Ormecon patents, in return, Ormecon got a minority shareholder position in Panipol 2001 (March) Zipperling grants a license to Bayer for their conductive polymer PEDOT („Baytron P“) which infringed basic Zipperling patents; press release and article in "Chemical Week"; later, „Baytron“ was marketed by the former Bayer subsidiary H.C. Starck, which was taken over by Heraeus, now their PEDT is marketed under „Clevios“ tradename 2000 (August) Ormecon / Zipperling grant a license to DuPont (USA); the license agreement replaced a former cooperation agreement which started in 1998; in a subcontract type of R+D project, Ormecon (based on the license agreement) resolved a serious production problem DuPont had while using Polyaniline 1999 - Wessling tries to establish a Joint Venture in China (ChangChun), together with the Chinese Academy of Science 2001 (Univ. of ChangChun); the attempt fails in spite of intensive negotiations, because the JiLin Province Government requires also transfer of technology, not only intermediate products; Wessling refuses, and even a final negotiation round during 2001 an official visit to China as a member of the business delegation accompanying Germany's Federal Chancellor Gerhard Schroeder (hereanother article in German, and an older newslink) (Nov 2001) 2001 September 11: Wessling is in Wisconsin / US, he is actively involved in a Whooping Crane Recovery project he developed and supplied the technology how to communicate with the isolated-reared Whooping Crane chicks (more about crane vocalisation); the terrorists attack are seriously impacting Ormecon's financial basis, while for 2001, break even was already reached, 2002 (due to the collapsing market), Ormecon's financial status was affected 2003 (March) several Venture Capital Investor Funds under the leadership of Emerald Technology Ventures (former name „Sustainable Asset Management“) invest in Ormecon and receive 33% of the shares 2003 (July) Ormecon acquires the residues of the insolvent Unicron GmbH and establishes ORMECON CSN chemicals and surface finish subcontract production in Kirchheimbolanden, and acquires the remaining half of the ImSn business owned by the former marketing partner Florida Cirtech (USA) 2004 Ormecon grants a patent license to Nissan Chemicals Industries (Japan) and enters into a cooperation agreement with them; later, also a joint patent application is filed describing a joint invention 2004 (priority date Jan 23) patent application describing dispersions which allow the deposition of polyaniline (Organic Metal) films having a conductivity of higher than 300 S/cm; Ormecon later achieved even around 1,000 S/cm. 2004 first groundbreaking Nanofinish patent application; however, this process did not allow a visible surface nanofinish, also during reflow not stable against discoloration, hence research continued and resulted in 2006 (priority date October 6) in the final Nanofinish process, here described in a technical magazine; the process was laterintroduced into the market by Enthone under the trademarks OrmeSTAR Ultra and ENTEK OM, resp. 2005 - in a serie of joint research projects with Prof. Krichnichnyi, focussing on EPR studies, it was possible to measure 2006 the intrinsic conductivity of the inner core of the primary particles of Ormecon's Organic Metal Polyaniline, it was found to be in the range of several 1,000 to several 10,000 S/cm (possibly 65,000 S/cm), 3 papers resulted, 2005, 2006 (1) and 2006 (2). 2005 (priority date Aug 19) patent application describing a new hole injection layer for polymer OLEDs (PLEDs) which deliver a much higher stability; the principle of the invention is that a Polyaniline-Indium complex is formed which strongly reduces the tendency of the ITO to become degraded. 2005 (April) B. Wessling decides to intensively work in China in order to save the just only a few years old China ORMECON CSN business which was in a critical stage; 2006 Ormecon China is established as a wholly owned foreign entity (registred in Nantong); in 2007 China has become the country with the biggest turnover (in CSN finish), surpassing Korea which was No. 1 since 2001 2007 Wessling starts learning Chinese 2011 he describes his personal and business experiences in China in a book ("Here they call me 'Laowei'"), in the meantime available in 2 German and 2 English editions, 1 English edition was published in China by the BeiJing located China Intercontinental Press", available from these sources and from the author 2008 September 3rd: Enthone acquires 100% of the shares in Ormecon GmbH; for some period of time, Ormecon continues to exist as a company (Enthone GmbH subsidiary), later it is merged with Enthone GmbH; at the time of acquisition, Ormecon has more than 60 employees, an already well established business with ORMECON CSN in Europe, USA, China, Korea and Japan (including CSN subcontracting facilities in Germany, USA, Korea, Japan and China), and an emerging corrosion protection business, mainly in Germany, Japan and Brazil 2009 on SMTA (a technical conference focussing on assembly), presentation of OrmeSTAR Ultra assembly properties 2010 further publications about Nanofinish technology, e.g. this one, also the Immersion Tin process ORMECON CSN was successfully improved: full solderability with only 30% of the previously necessary Tin thickness (SMTA 2010) 2011 HKPCA show: presentation about Nanofinish 2010 parallel to the beginning introduction of the Nanofinish technology, a powerful anti- corrosion wax was developed at Enthone NanoScience Center Ammersbek (the former Ormecon site), with intensive scientific and technological support and advice by B. Wessling; a joint patent application was filed together with Nissan Motors where the performance tests had been run 2010 the biannual ICSM was held in Kyoto (Japan), Wessling gave an oral presentation "New insight into Organic Metal Polyaniline Morphology and Structure" which was later published as full paper in "Polymers" 2011 the major competitor for ORMECON CSN, the German company Atotech (a Total subsidiary) entered into a license agreementwith Enthone as their Immersion Tin process infringed an older Enthone patent 2011 Nov 9-11: TPCA PCB trade show and technical conference are also used for the promotion of ORMECON CSN and Nanofinish 2012 (August) Dr. Bernhard Wessling establishes his own technology consulting company in China 2013 (February) his attempts to learn Chinese have lead to at least some satisfactory level, here presenting 2 jokes in Chinese on the Enthone Annual Dinner The trademarks (formerly established by Ormecon GmbH) ORMECON, ORMECON CSN, ORGANIC METAL, ORGANIC NANOMETAL, CORRPASSIV, NANOFINISH are owned by Enthone, as well as OrmeSTAR Ultra and ENTEK OM (established by Enthone). Products based on the technology developed by Ormecon GmbH are now available from Enthone.