ATTENTION JOB SEEKERS!!

If you’ve got the air fare & the time you can go to the 2012 Spring

National ACS Meeting in San Diego to attend the ACS sponsored Career Fair..... But you don’t have to!!!!

Attend the career fair virtually on March 26-27 Register at http://

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The Alembic

VOLUME 39, NUMBER 2 MARCH 2012

2012 ACS - CWS

Mini-Directory

Chair

Dale Pillsbury

796N Pripps Road

Park Falls, WI 54552

Phone: (715) 583-4426

E-mail: hollyanddale@aol.com

Chair-Elect Lori Lepak

Department of Chemistry

Univ. Wisc. - Stevens Point

Stevens Point, WI 54481

Phone: (315) 224-1190

E-mail: Lori.Lepak@uwsp.edu

Immediate Past Chair

Robin Tanke

Department of Chemistry

Univ. Wisc. - Stevens Point

Stevens Point, WI 54481

Phone: (715) 346-4325

E-mail: rtanke@uwsp.edu

Secretary - Treasurer Tipton Randall

Phone: (715) 720-1969

E-mail: trandall@clearwire.net

Councilor C. Marvin Lang

Phone (715) 346-3609

Email: cmlang@uwsp.edu

Alternate Councilor James Brummer

Phone: (715) 346-2888

E-mail: jbrummer@uwsp.edu

Newsletter Editor Dale Pillsbury

Address & contact: see Chair

The Chair’s Corner - Variety is the Spice of Life

See page 2 for directions to the Palms Supper Club

See page 3 for Dr. Gargulak’s abstract and biography

Dale

March 2012 CWS ACS Meeting

“ The BALI Pretreatment Process: ” Pilot / Demo phase for conversion of biomass

to sugar and specialty lignin streams

A Plant Tour & Presentation

Speaker: Dr. Jerry Gargulak, Research Manager

Borregaard LignoTech, Rothschild, WI

Where: Borregaard LignoTech Facility

100 Grand Avenue

Rothschild, WI 54474

When: 7:30 PM Tuesday, March 13, 2012

Pre-meeting social (5:30 pm) and dinner (6:00 pm) will be held at the

Palms Supper Club, 5912 Business 51 S, Schofield, WI, 54476. Please

contact Jerry Gargulak at jerry.gargulak@borregaard.com, by Noon on

Monday, March 12th to make reservations

PLEASE

NOTE! Plant tour space is limited to

25 people on a first come basis

February’s speaker, Dr. Jeff Bryan, gave a well-received talk on depleted uranium.

Dr. Bryan then moved on to the NE WI section and finally the Milwaukee section,

the first of our three jointly-coordinated tours of ACS Speakers. This month’s meet-

ing features a tour of the LignoTech facility in Rothschild together with a talk by

section member Jerry Gargulak and it promises to be equally enjoyable. Please note

there is a 25-person limit on the tour guests, so make your reservations early.

On pages 2, 4 and 5 you’ll see a photo spread from a Chemistry exhibit created by

Dr. Mike Zach as part of UW-SP Continuing Education’s annual Women & Science

Day. Your section helped to finance this exhibit as part of its public outreach role.

Finally, on pages 6 and 7, I offer a piece on the story of Teflon; it really was a col-

laboration of coincidences.

Volume 39, number 2 The Alembic 2012

Directions to Palms Supper Club and LignoTech Palms Supper Club 1. From US 51/I39 take Exit 187 onto WI 29 E & go over the WI River.

2. Take WI 29 E to Exit 171, turning right onto Business Route 51 N (BR

51 N). This is also known as Grand Ave at this point, but the street name

changes further on. Stay with the designation BR 51 N

3. Proceed on BR 51 N about 0.6-0.7 miles and you’ll see Palms Supper

Club on your left (next to McDonalds).

4. Since BR 51 N and BR 51 S are divided, continue on BR 51 N to the

next cross street (Neupert Ave), then go back on BR 51 S to the Palms

Supper Club, 5912 BR 51 S Schofield, WI (ph 715-359-2200)

LignoTech 5. Continue south on BR 51S about 1.5 miles, going under WI

29 E to LignoTech, which is on your right at 100 Grand Ave,

Rothschild, WI

X

US 51

BR 51N

WI

29E

BR 51S

Neupert Ave

WI river

Palms

Supper

Club

XLignoTech

exit

187exit

171

2012 UWSP Women & Science

Day

A Campus-wide Production Organized by UW– Stevens

Point’s Continuing Education

The Women and Science Day is an annual event organized by UW-SP Continuing Education. Aimed at girls in 7th

and 8th grade, it involves numerous hands-on workshops exploring a wide variety of careers in science and runs from

early morning through mid-afternoon with 600 girls participating this year. Dr. Mike Zach created this year’s Chemis-

try Department exhibit with help from 19 UW-SP student volunteers. The exhibit taught the girls about interference

patterns when drops of clear nail polish are added to water to create thin films of polymer as the ethyl acetate solvent

dissolves. Placing the thin film of polymer on black Tyvek really brought out the colors. The girls also turned tita-

nium foil into earrings and key chains by heating the foil to create a number of oxide layers which again set up inter-

ference patterns and created attractive multi-colored metal which could be shaped into earrings or key chains.

More photos on pages 4 & 5

Page 2

Volume 39, number 2 The Alembic 2012

Page 3

A Plant Tour & Presentation

March 2012 CWS ACS Meeting

“ The BALI Pretreatment Process: ”

Pilot / Demo phase for conversion of biomass

to sugar and specialty lignin streams

Speaker: Dr. Jerry Gargulak, Research Manager

Borregaard LignoTech, Rothschild, WI

Where: Borregaard LignoTech Facility

100 Grand Avenue

Rothschild, WI 54474

When: 7:30 PM Tuesday, March 13, 2012

Please Note: Plant Tour Space is

Limited to 25 People on a First

Come Basis, So Make Your Reservations Early

Pre-meeting social (5:30 pm) and dinner (6:00 pm) will be held at the Palms Supper Club, 5912 Busi-

ness 51 S Schofield, WI, 54476. Please contact Jerry Gargulak at jerry.gargulak@borregaard.com, by

Noon on Monday, March 12th to make reservations

ABSTRACT Over the last 50 years, the Borregaard pulp mill has evolved into one of the world's most advanced operat-

ing biorefineries. Borregaard has developed a new separation and pretreatment process for recalcitrant lignocellulosic bio-

mass. This process, called BALI, allows for easy conversion of cellulose to glucose with low cellulase enzyme consump-

tion combined with attractive process economics. This process addresses three of the main challenges identified by other

pretreatment technologies: 1) Lignin binds to enzymes, requiring higher dosing and preventing recycling. 2) Impure and

strongly condensed lignins are unattractive for most lignin applications and 3) Low yields of value-added products and

high yields of products valued only for their energy content result in an unfavorable mass balance and process economy.

The BALI pretreatment process solves these challenges simultaneously, and has resulted in a sulfite-based pretreatment

process that yields a water soluble lignin with identified applications and a cellulose pulp that can be hydrolyzed with en-

zymes under industrially relevant conditions. Status of the 50 kg/h pilot plant will be presented.

BIOGRAPHY Dr. Jerry Gargulak is a graduate of the University of Wisconsin, Eau Claire (88,

ACS Chemistry) and the University of Minnesota (93, PhD, Organic Chemistry). In 1996 Dr. Gar-

gulak became Research Manager at Borregaard LignoTech’s US operation center in Rothschild,

WI. Since that time he has worked to develop useful modifications to lignin with the goal to de-

velop new industrial applications for this biopolymer. He has developed lignin technology for use

in mining and cement manufacture, including environmentally friendly reagents for ore processing

that replace sodium cyanide, and additives that allow for lower carbon emissions in the manufac-

ture of cement. His current responsibilities include investigation of new opportunities for Borre-

gaard related to the development of value-added materials derived from bio-refining of lignocellu-

losics.

SITE HISTORY The facility in Rothschild was one of the earliest to recognize the potential value in spent pulping liq-

uors. Over a number of years many processes have been commercialized at this site, including the vanillin process, uses

in concrete, and the Howard process, to name a few. The site has had a number of owners, including Marathon, American

Can Company, and Reed Lignin. In 1991 Borregaard Industries Ltd purchased the site from Daishowa. The Lignotech

web site, www.lignotech.com, gives an excellent summary of the applications where their products find commercial ap-

plication, as well as the overall Borregaard LignoTech commercial enterprise.

Volume 39, number 2 The Alembic 2012

Left Dr. Michael Zach, UWSP Chemistry Dept Staff &

chemistry student, Casey Biebel (right), assist a student to

attach the earring hook onto the newly made colored titanium

earring.

Dr. Zach created the exhibit program, which was financially

supported by the Central WI local ACS section, the UW-SP

Chemistry Department & Dr. Zach’s NSF CAREER Award

which helps to supplement outreach activities.

Right Life Sciences Major, Nikki Rukamp (left), con-

gratulates a student for learning how cool it is to make

fantastically colored thin films of clear nail polish—an

unexpected discovery from a very common cosmetic

product.

Dr. Zach provided handouts with added details of the

chemistry and physics behind what the girls were observ-

ing, giving more depth to the learning experience.

This is UWSP’s Women & Science Day!

Page 4

UW-SP Women and Science Day photos - continued from page 2

Volume 39, number 2 The Alembic 2012

Left Two students are learning how to use jeweler’s

torches to evenly heat titanium. The reaction with air

forms titanium dioxide, which is colorless. The tem-

perature and duration of heating causes different

thicknesses of the film. The resulting films are in-

tensely colored, commonly showing blues, purples

golds and reds.

Right A girl grinds through

the brightly colored titanium

dioxide layer to engrave the

oxidized titanium foil.

Left Another participant

uses a second torch to lightly

heat the engraved titanium. A

more gentle heating causes

freshly exposed titanium from

the engraving to oxidize. This

2-step oxidation causes differ-

ent colors from the overall

background color and gives

nicely contrasting colors.

Above Camaraderie, fun and learning; these girls proudly show off their handicrafts. It is clear that everyone

enjoyed making their key chains and earrings. By having so much fun while learning the chemistry and phys-

ics behind the fantastic colors on titanium, all of the UWSP staff and volunteers hope to encourage bright stu-

dents to continue learning. Events like this are helping more students become more science savvy and it is

hoped some may choose to become future Women in Science! Page 5

Page 6

Volume 39, number 2 The Alembic 2012

The Teflon Story: A Collaboration of Coincidences? Setting the Stage In 1916, the Guardian Frigerator Company was started in Fort Wayne, IN to build the first self-

contained refrigerators. William C. Durant, the founder of General Motors, seeing the increasing popularity of refrigera-

tors, personally purchased the company in 1918. By 1919, GM owned the company, which had been renamed Frigidaire.

The manufacturing operations were moved to Detroit and GM’s engineering resources were focused on the project. By

1926 Frigidaire was set up as a separate GM division in Dayton, OH. While more people were purchasing refrigerators

the available refrigerants (ammonia, sulfur dioxide and methyl chloride) were all toxic and/or corrosive and many home-

owners felt safer with ice boxes. In 1928 Charles F. Kettering, head of GM’s Research Laboratories, located in Dayton,

directed Thomas Midgley, Jr. (of tetraethyl lead fame) to find the solution to the refrigerant problem. Impetus for the

project came from a rash of deaths in 1929 in Chicago related to refrigerant leaks. Clarence Birdseye’s test-marketing of

frozen foods in 1930, using Frigidaire-made display cases, presaged another refrigeration market opportunity.

Midgley quickly turned to polyhalogenated compounds, given these were rather volatile, but were not flammable and

were relatively inert. The high energy of the C-F bond increased stability, while also increasing volatility. This led Midg-

ley to focus on chlorofluoromethanes shortly after the project started in 1928.

Dichlorodifluoromethane (Freon 12) was an outstanding ini-

tial choice, based on a reasonable degree of volatility, mak-

ing compressing relatively easy. It was also very stable, hav-

ing no H-C-Cl moieties which could undergo α-elimination

to highly reactive carbenes. Midgley introduced the public to Freon 12 at the 1930 annual meeting of the American

Chemical Society, where he breathed some in and exhaled it to extinguish a candle flame to show it was neither toxic nor

flammable.

Roy Plunkett & Jack Rebok Having laid the groundwork, in 1930 GM teamed up with DuPont to create a joint venture

known as Kinetic Chemicals. During the early 1930s, Thomas Midgley brought samples of Freon 11 (CCl3F) and Freon

12 (CCl2F2) to DuPont’s Jackson Laboratories near their Deepwater, NJ plant. Kinetic Chemicals rather quickly came up

with a series of improved Freons, based on fluorinated, chlorinated ethane, with Freon 114 (F2CCl-CClF2) being the best

seller. The Freons not only worked well as refrigerants, they found widespread use as aerosol spray propellants. Dr. Roy

Plunkett, a recent Ohio State graduate, was hired in 1936 and he and his technician, Jack Rebok, were assigned to the

Kinetic Chemical Freon project to try to add HCl to tetrafluoroethylene to make F2CCl-CHF2 to see if this would be an

even better refrigerant. They synthesized 100 lbs of tetrafluoroethylene from HCF2Cl, which was itself made from HF

and chloroform using the Swarts reaction* wherein the chlorines in a polychlorocarbon are substituted with a fluorine by

the action of HF and a catalyst made from antimony trifluoride together with Cl2 or antimony pentachloride:

Sb2O3 + 6HF(g) → 2SbF3 + 3 H2O SbF3 + Cl2 [or SbCl5 ] → SbF3Cl2 (actual catalyst)

F/Cl substitution (driven by strength of C-F bond) Pyrolysis (650-700º C, in a Pt Tube)

HCCl3 + 2HF + SbF3Cl2 → HCF2Cl + 2HCl 2 HCF2Cl → 2 HCl (via α-elimination) + [2 :CF2 ]→ F2C=CF2

Plunkett and Rebok stored their tetrafluoroethylene in several steel cylinders cooled in dry ice. Using a valve, they added

what they needed for a given reaction, checking the charge amount by the decreased weight of the steel cylinder. On

April 6, 1938, they attempted to add some tetrafluoroethylene from a cylinder, but found they were unable to release any

gas. The official story is that Plunkett tried to clean out the valve with a wire and found only a small amount of a waxy

white solid. He determined by weight that the cylinder had the expected amount of material still in it. The cylinder was

carefully sawed open to reveal white waxy solid coating the interior wall. He characterized the material as being

polytetrafluoroethylene. The strange material was found to have a remarkable resistance to corrosive chemicals, was in-

soluble in virtually everything, had a very high melting point and possessed an extraordinarily low coefficient of friction.

Plunkett hypothesized F2C=CF2 polymerization must have occurred in the cylinder. With additional work, he was able

carry out the polymerization reaction in a controlled manner and filed a patent on July 1, 1939 (granted in 1941).

There is no question that Plunkett deserves credit for recognizing polytetrafluoroethylene for what it was once the cylin-

der was opened, and for his preliminary characterization of the new polymer. The dogma of the day said such highly

halogenated olefins would not undergo polymerization. Plunkett was also diligent enough to pursue repeating the

polymerization under controlled conditions and was sharp enough to patent the material as quickly as he did. The only

bone of contention is who actually pushed to have the cylinder sawed open to reveal the first known batch of what was to

Properties CCl3F CCl2F2 CClF3 CHCl2F CHClF2

bp (°C) 23 -29.8 -81 8.9 -40.8

∆ fH° 25°C (kJ/mol) -289 -492 -708 -283 -482

Frédéric Swarts (1866 - 1940) A Belgian chemist who prepared the first chlorofluorcarbon, CF2Cl2, as

well as several other related compounds from polychlorocarbons and the SbF3Cl2 catalyst.

become known as Teflon. There are references noting that Plunkett originally said to just use

another cylinder and later it was the technician, Jack Rebok, who weighed the balky cylinder,

found it to have the correct weight and recommended to Plunkett that they open it to find out

what happened. Plunkett correctly received considerable credit at DuPont and was inducted into

the Plastics Hall of Fame in 1973 and the Inventor’s Hall of Fame in 1985. In 1939, after work-

ing for DuPont for only 3 years, Plunkett was promoted to chemical supervisor of DuPont’s

tetraethyl lead manufacture at the Chambers Works where he stayed until 1952. He then di-

rected Freon production at DuPont before retiring in 1975. Technician Jack Rebok did not re-

ceive any particular credit for his part in the discovery of Teflon, but on his retirement, a man-

ager from another DuPont department gave Rebok a considerable financial award from his own

budget. It seems that all too often technician’s contributions are minimized.

Teflon really was “a

horse of a different

color”. The monomer,

tetrafluoroethylene

(TFE), was very unpleasant to handle. It was

highly sensitive to oxidation, producing explo-

sive peroxides which could, and did, result in

explosions during storage. It was often handled

as a mixture in an inert gas, since spontaneous

explosions to carbon and CF4 also occurred.

The process flowsheet is given to the right. To

make a suitable product, the TFE monomer,

created in a hellish pyrolysis at 700º C, had to

be 99.9999% pure (1 ppm impurity).

The polymerization itself is highly exothermic

and is usually carried out in purified water con-

taining a soluble peroxide catalyst, e.g. ammo-

nium persulfate or disuccinic acid peroxide. By

using no surfactant and strong agitation, a

stringy polymer is made, which is converted to granular particles by a chopper. Fine powders and dispersions are made

using a surfactant and, in contrast to many emulsion polymerizations, low speed agitation is employed - the surfactant

providing a high degree of monomer dispersal. Ammonium perfluorooctanoate is the preferred surfactant. However, like

the perfluorooctylsulfonyl moieties (see my Scotchgard vignette in the February Alembic), perfluorooctanoate can be

bioaccumulated in humans. It is not clear how deleterious to health these residues are, but in 2002 DuPont initiated com-

mercial production of “greener” fluorocarbon polymers using supercritical CO2 technology. However, to date this tech-

nology appears to be restricted to copolymer products, and not the polytetrafluoroethylene homopolymer itself.

Learning how to process Telfon was another major hurdle for DuPont, which started commercial production of the poly-

mer at their Arlington, NJ pilot plant. Given the complexity involved, it is unlikely that Teflon processing would have

developed as quickly as it did, if it wasn’t critical to the Allies in WWII. It was used for nose cones of proximity fuzes

and for the handling of fluorine and UF6 in the Manhattan Project. It was also used as a very low-dielectric coating for

wires in cables handling microwave radiation used in US night-bomber radar sets — nothing else worked!

Traditional solvents do not dissolve Teflon and it starts to decompose somewhat below its ~327º C melting point, so the

majority of commercial processing of Teflon had to employ very unconventional polymer processing techniques. In fact,

the most common techniques used for processing Telfon are those associated with metal-powder metallurgy.

One of these techniques is sintering, which involves holding a fine powder at a temperature

well below its melting point, usually in a confined space under high pressure. Sintering re-

sults in solid state diffusion, which binds the particles very solidly together. It is often used

in metallurgy to form solid objects from very-high-melting solids, e.g. molybdenum or

tungsten powders. Sintering is responsible for the bonding of ice cubes stored in a freezer,

as well as the firing of ceramic pottery in a kiln. The driving force for the sintering process

is a reduction of the surface energy of the particles, caused by decreasing their vapor-solid

interfaces. Sintering was employed to make the non-stick fry pans that became so popular worldwide. They were in-

vented in France by an engineer, Marc Grègoire, who coated his fishing equipment with Teflon, and then, at the request

of his wife, coated some of her cooking pans and patented the process - the rest is history.

Volume 39, number 2 The Alembic 2012

Lewis Acid

Catalyst

Chloroform

HF

CHClF2

Reactor

HCl

Chilled Still

Scrubber

HFperfluorpropylene

& other higher MW byproducts

Platinum

Tube Cracker

Recycle to

Cracker

Chilled Still

HCl +

Tetrafluoro-

ethylene

Scrubber with Dryer

on Top

HCl

Purified Dry Tetrafluoro-

ethylene

Ammonium Perfluorooctanoate

Surfactant for Fine Powder or Dispersions

Ammonium Persulfate

or Disuccinic acid Peroxide Catalyst

Polymerization

Reactor

Chopper

Teflon

Dispersion

Storage

Teflon

Particle or Powder

Storage

Dryer

Typical Process Flowsheet Teflon Resins

Chlorodifluoro-

methane

Page 7

Reenactment of the 1938 dis-covery of Teflon. Left to right:

Jack Rebok, Robert McHarness, & Roy Plunkett Hagley Museum and Library.

Dale

Volume 39, number 2 The Alembic 2012

The Alembic (March 2012)

Newsletter of the Central Wisconsin Section, ACS

c/o Chemistry Department (#605516)

University of Wisconsin – Stevens Point

Stevens Point, WI 54481

Member Address Label

Page 8

Central Wisconsin Section, ACS Meetings and Programs - 2012

Date (Day) Location Speaker/Event Host

March 13, 2012 LignoTech, Rothschild LignoTech Tour Jerry Gargulak

April 18, 2012 Stevens Point Willam Carroll OxyChem ( A CS ) Robin Tanke

May 2012 Eau Claire Awards Banquet Dave Lewis

Sept 2012 Stevens Point 40th Anniversary of Section Marv Lang

Oct 2012 TBA Dr. David Wiemer TBA

Mark the above dates and locations on your calendar; plan now to attend and participate in the Section’s various meetings and activities. Future issues of the Alembic will give exact lo-cations and arrangements for these meetings. Of further interest are the following national and regional events:

Spring National Meeting, San Diego, CA - March 25-29, 2012

Chemists Celebrate Earth “ Week ” ( Stevens Point ) - April 18, 2012

ACS 43rd Central Regional Meeting, Dearborn, MI - June 5-8, 2012

M

ark your calendar … plan to come:

Dr. Je

rry Gargulak, Research Manager,

LignoTech, Rothschild, W

I presents

“ The BALI Pretreatment Process: ”

at the

LignoTech Plant, Rothschild, W

I

Tuesday, M

arch 13 at 7:30 PM