Monday, July 4, 2022

Outline For A Review Of Jim Baggott's excellent book: "Perfect Symmetry: The Accidental Discovery of Buckminsterfullerene "

Some important points I would like to write about, showing the public how science works.  I don't think most people are getting the stories about these aspects of science.

I got these from reading Jim Baggott's wonderful book:  "Perfect Symmetry: The Accidental Discovery of Buckminsterfullerene".  


1) buckyballs, which are chemistry, were discovered by astronomers looking at OBSERVATIONS of phenomena in the real world.  Interstellar dust or molecules made inside machines and soot, rather than the organic chemists theorizing for decades about abstract shapes.

2) Kroto came and visited Smalley's lab, where he had two grad students. When the students revved up their machine to make interstellar organic dust, they found such preposterous results that they were afraid to show them to their Smalley for fear he would think they broke his machine or something.  But Kroto would hang out with them and that easy going relationship encouraged them to show him their crazy C60 results which then got the ball rolling.

3) some of the investigators were really on a good track to finding the stuff, but they were stymmied by poor funding and malfunctioning machinery delaying their resuls.

4) fascinating tension between investigators sharing enough info between labs to edge each other onto the right track but trying not to share too much so that the other lab would discover it first!

5) the nitty gritty details of the techniques the different investigators had to learn in order to get results.  Many were working outside the fields they had trained in.

6) the role of grad students had to play, in trying goofy things that ultimately led to new results.


7) how having ALL the different kinds of labs in 1 intercommunicating space/culture at IBM allowed them to put results together so quickly

8) caution the investigators displayed in not wanting to publish wild results until they were tested solidly in a few different ways.  that is how science becomes more certain of their results and builds a solid foundation.

BUT HERE IS THE DEAL, THIS IS WHY WE THINK OF C60 AS ***REAL*** SO MANY LABS FROM SO MANY ANGLES GET RESULTS THAT JIVE: mass spec, specific signal at 60 70, geometry, huckel theory, La in cages, suggestive uv spec, producing it from laser ablation and cooling, from carbon arc to soot, laser ablation... IR spec, tons of calculations from diff ideas, chem and sublimation purification, raman spec, NMR of 60 and of 70, crystalization, electron diffrac to get spheres, scanning tunneling microscope to get spheres...

AND AFTER 300 YEARS OF KNOWING HOW EASY IT IS TO BE FOOLED, THESE RESULTS ARE DONE OVER AND OVER AGAIN BY DIFF PEOPLE WITH SLIGHTLY DIFF TECHNIQUES  CO9NSTANTLY CHECKING EACH OTHER SO YOU KNOW YOU ARE NOT CHASING WILD GOOSE

ALSO TO REALISE THIS ISN'T SUCH AN ARTIFICIAL SPECIALIZED STATE OF MATTER BUT IT CAN FORM QUITE EASILY IN A NUMBER OF DIFFERENT ENVIRONS...

9) how LONG science takes to do.

10) should we redesign things to work like IBM labs so things happen quicker or is it ALL RIGHT that science proceeds at the pace it does.  Or even, did things ultimately depend on the fact that enough different investigators were working independantly?

11) Interstellar dust, buckminsterfullerenes, the detection of them... is really cool science.

12) the role that communication of ideas, results, conversation, conferences, critique,  plays in science.  the community of conversation is, in my opinion, what defines modern science.  There were at least 6 different teams interacting on this over a period of about 15 years.

i think these are all important aspects of science that the public is ignorant of, but should really know about.

 

 

ok, i need to grokk these notes

review: from Baggott


1927 darcy thomson shows radiolaria produce cages with hexagons but need pentagons too

of course a ton of soot chem

1966
David Jones publishes a whimsy as Daedalus that he can make giant graphite gasbags by adding defects to the graphite and it would be a new state of matter density between gas and condensed

1982
after reading thompson, he elaborates and uses euler formula to show he needs introduce only 12 pentagons

NO ONE NOTICES?

1952
fullers domes were first constructed

1960
Roger Bacon grows graphite whiskers in carbon arc at union carbide pub in jnl applied physics, from elec mic and xray diff decided these were spirally scrolled graphite sheets into micron wide cm long whiskers

NOT FOLLOWED UP?

1963 hoard et all find B60 with a B24 inside  boron is crazy theres' tons of boron geometry, no?


1966
Wayne Barth and Richard Lawton umich synthesise corannulene with pentagon surrounded by 5 hexagons.  is it aromatic?  chemists believed aromatic had to be planar, yes it was but xray diff said bowl shape!

Eiji Osawa was wondering about non planar aromatics, and read this and wondered all the way to sphere?  saw kids soccer ball, bingo, published an abstract in japanese journal, and then with z. yoshida published ideas in book 1971  he even checked huckel theory, yes it checked.  but he and other japanese chemists who read this were thinking of mundane problem: how would you synthesise in ordinary lab procedures.  THEY WEREN'T THINKING BIG ENOUGH, BROAD ENOUGH WAS IT A NATURAL FORM OF CARBON?

>>>SO ULTIMATELY THIS DISCOVERY COMES FROM OBSERVATION, OBSERVATIONS OF NATURE, OF CURIOUS SPECTRA IN ASTRONOMY!  and kroto, kratchmer, huffman, curl and smaley heath and obrien are NOT orgo chemists!


1968
Goresy, Donnay looking at shiny samples alternating with graphite in meteorite crater suggested new form of carbon called carbyne

whittaker 78 heats graphite to white substance at high temp and imagines carbynes alternating single and triple bonds


1973
Bochvar and Gal'pern also imagine C60 and do the Huckel calculations even imagine a whole new class of such molecules pub in proceedings acad sci ussr
tx english in russian chemical reviews 1984

1980
sumio iijima finds elec micrograph of onion shaped carbon strtucts from carbon deposition at NEC corp fund research div in japan and thinks its graphite laryers around a structure with pentagons.

EXPLORE THIS ROUTE NOT TAKEN

no mention of if he published this till 1987

BY 1991 he discovers nanotubes

1981
Robert Davidson of dupont, delaware also imagines it and calculates, in theoretical chimica acta 1981 obscure

jul1981
Orville chapman visits U. erhlengin and francois diederich decides to synthesis C60 gets national science foundation grant and 5 grad students 81-85 during this time discussing with organic chem community skeptical, he complains orgo chem community is stale turned inward

by 1985 Diederich with rubin, knobler, Robert Whetten, schriver, Houk, Li is synthesizing C18 to C30 but the large rings not stable and turn into some kind of forms of C48 50 60 70  SOME ODD RESULTS DID THEY FINALLY FIGURE OUT WHAT THEY WERE GETTING?

1983
leo paquette et al synthesise dodecahedrane

1985
Anthony haymet ucal berkely doing huckel calcs on C60 INDEPENDANTLY?

1985
bloomfield, geusic (ex student of smalley) freeman and brown at at&t bell labs were working on similar experiments mass specx with ion clusters they got diff pos and neg ion distributions no special C60

1986
Robert Whetten et all of ucla dep chemm biochem solid state also got mass spec with odds and evens and signatures of magic numbers 50 60 70 but thot this was breakup process not special structures


ALOT OF PEOPLE WERE WORKING ON THIS, ONLY SOME GOT ALL THE WAY


MAIN STORY

1975
Harry Kroto is a microwave spectroscopist! looking for interstellar orgo molecs polyenes

production on surfaces or plasmas of red giants
82 microwave spec show c chains up to 11

sees 1963 paper on carbon arc producing C molecules up to C33  hintenberger, franzen, schuy

their graph stops at C33, why did they not continue up to even numbered Cs?  QQQ


what are diffuse interstellar bands?  found in visible spectrum of starlight, instead of sharp absorption lines found in solar spectrum we have bands, in 30s were shown to be interstellar

Douglas suggests long C molecules  by mid 1970s there are 40 unexplained bands  associated with dust grains maybe smaller particles on the dust grains

radio astronomy detects molecules with dipoles,

rotations vibrations of long molecules picked up in microwave


1976
Wolfgang Kratschmer physics radiation damage on solids joins Donald Huffman physics spec study of interstellar dust to study spectroscopy of possible interstellar dust analogs

dust is <1%interstellar medium but dimms light by 1/2 every 3000lightyears of travel.  by absorption and scattering it preferentially dimms uv, blue, hence reddening

similar to our own atmosphere?

particle sizes from few nm (uv) to 100nm visible, to small amount of micron (IR)

in interstellar space with 1 atom per cc dust particles might be 100m apart

thyere are 40 diffuse interstellar bands in visible but huffman notes some other features:

some absorption features in 3-9micron in IR, and 217nano feature, he began exploring in spare time, not much FUNDING

this harder than kroto's work on microwave spectra, they are distinctive, this stuff more vague

kratschmer decides start with 9.7micron band, maybe olivines, to get match bombard olivine crystals with high energy to make amorphous

next 3.1micron band: ice?  make it amorphous but particles fairly large size, coating dust?

1973
next huffman wants to tackle 217nano feature, thinks graphite, begins carbon evaporation machine to examine soot some match but not good, over years huffman chips away, decides factors of size, crystalinity, shapes of particles play role

could be more than just C, but Huffman wants to keep simple

1982
he and kratcscher and Norbert Sorg begin try make small round graphite particleds in graphite tube evaporator jar, with vacuum pump.  controlling pressure seen to be key to particle formation size, but needed some gas to cool the carbon into soot

they didn't quite get the 217nano feature looking for,  thot particles clumping too much,

 but also: every now and then on smooth curve predicted for soot, they get some humps at 215 265 and 340 nanos

kratschmer dismayed, thot contaminants, huffman intriqued

their IR spectrometer was not great, no good results.  ACCESS TO GOOD EQUIPMENT, shift priorities...

they worked at their camel humps but no good results offered ideas.  they never raised pressure of gas >20torr

raman scattering spec also showed interesting features in he camel samples

are they thinking carbyne?

they gave up in 83


1984
kroto visits Bob Curl in houston, who had been working with Rick Smalley created wonderful machine to produce and study new molecules of semiconducting materials

this lab was well equipped, smalley developed big lab but kept his fingers on the experiments, specialized in building the machinery, macine was unique cause used lasers to blast stuff into small molecules in a cool enough environment to measure good spectra not too noisy with too many energetic modes

then onto time of flight mass spec

kroto of course wanted to try carbon, as this machine would mimic red giant atmosph, smalley didn't think anything new would be found


1984
Rohlfing, Cox, Kaldor at exon get a mass spec of blasting graphite with laser: find carbon clusters from 2 to 190!

Pat langridge-smith (who had been at smalley lab) found the paper gave it to tony stace (worked with noble element clusters) who gave it to Kroto

Rohlfing et al got a copy of Smalley's AP2 in 82!

first half of spectrum repeats hintenbergers results, alternating peaks in even odd number C atoms some odds being tallest 11 15 19 23 trail off at C33

but then rise again at C38 and show even peaks, capping at C60 and falling again, NO signals from odd Cs

R et al had no explanation for only evens, carbyne?  i.e. CzC units

but more measurements could be done, kroto wanted to try

Smalley saw paper, and said nah, don't want to let that team do it.

Kroto is still interested in finding cyanopolyenes cause they are dipoles and can be found in interstellar space


july84
Kaldor presents results at conference, Huffman and Kratschmer see it, they present some results on finding low C chains, find the large cluster results curious but

they didn't mention their camel humps (huffman had thot camel humps carbyne?)

[[SO THIS KEPT THEM INTERESTED?]

nobody remarked upon the C60, 70 signals


aug85
the app2 is finally available for kroto.  jim heath and sean o'brien are students with smalley.  yuan liu and quing ling zhang also joined.

liu and zhang are able to repeat exon results, they did not report to anyone one run where 60 70 signals out the roof, just recorded in the log

they and heath begin 2 photon resonance spec and find smaller molecules <25 respond, so they can test douglas'  ideas of long molecs in red giant clouds

working under smalley was difficult and students feared showing weird results unless they could explain them

they met.  kroto: aim for HC33N and measure spec to see if in interstellar space

Kroto begins to gets to know the students  high C60 result still hidden in student log

heath and obrien worked the machnine.  

heath and kroto first run, heath curious about arrival times of diff molecs (the mass spec comes from avberageing many runs)  heath adds thermalization nozzle to let all particles thermalize together.

slight C60 signal but machine not working well

they meet, trying to imagine why even numbers.  smalley discusses dangling edges must be closed, rings?

next they try in H atmosphere the odd len Cs turn to even lengths, so Polyenes!  large even signals are a little stronger

kroto wanted to find cyanopolyenes, curl wanted to look for pure carbon molecs

Kroto had graphic art background

they all worked together as team long hours into night having discussions of all sorts of topics

finally they tried N, not interesting!

switched back to He for some reason this time they saw C60 off the scale and C70 following.  AH... THIS TIME KROTO WAS WITH THE STUDENTS, SMALLEY STAYS AWAY.  KROTO'S REL WITH STUDENTS HELPS SEE THE SIGNAL.

sep3
kroto brings results back to smalley and curl, finally they discuss.  why this very peculiar C60, 70 signal?

at this point they try imagine what made C60, 70 so stable, dangling ends must be joined?  why would a ring be only stable at 60?  a sphere? geodesic dome? they had only VAGUE notionsof the geometry and didn't understand what was needed to curl the graphite hexagon sheet into sphere.  kroto has vague memeory of geodesic toy with pentagons

they went back to N and did find cyanopolyenes up to 20, cool

kroto got his result, but they all were intrigued by the C60.  the students decided to find out why thge signal was so haphazardly produced

obrien and heath systematically found the C60 signal to be robust and dependent on pressure of He and timing of laser blast and cooling

heath finally found conditions which produced virtually all C60 with a little C70 tagging alonhg

obrien got tired of wondering what structure C60 was wanted to go back to GaAs exps

they decided to publish the cyanopolyene story but reluctant to publish the C60 until they had some notion of struct

heath and wife tried making a C60 from gummies and toothpicks, even tried includiing triangles with hexagons, coulnd't

smalley tried with paper hexagons, no.  what?  then rememberd kroto had mentioned pentagons, eventually, he found it.

[when did i know what a dodecahedron was?  well math book on platonic solids... but i made dodecahedron in boston in 86 AFTER this stuff was published? hmm]

Curl decdided to check if he could make a series of single and double bonds around the thing to satisfy carbon.  bingo

a call to the math department told them that they had just built themselves a SOCCER BALL oy duh duh!  HOW BLIND WE CAN BE!  

***(((QQQQ)))
but also... we already knew boron does this right???

now they were excited!

they published., reviewer suggested they look at Douglas and Huffman's work


they tried Iron in the cage, wouldn't go

NAILING IT

they tried lanthanum (heath favored it) they found it associated with C60 AND other large even numbered molecules, was this a whole FAMILY of cages?

exon group fought the buckyball interpretation

they do stuff, get lots of criticism

they couldn't get spec of C60 tho

exps show odd chains fragment by loosing C3s at a time, but smalley lab showed buckyballs loose C2s each time


apr1987
kroto and smalley split, kroto back to sussex
he got some funding, started with evapo machine, couldn't get a mass spec tho <<<<<<<<<

in 87 homann finds a 60C molec in ordinary soot formation, burning acetylene etc..

then iijima publishes his onion pictures from carbon arc process

by 89 cold fusion fiasco cools the waters and there is still no sample large enouigh to be analyuzed.  doubt


1985
lowell Lamb postgrad with background in computers tells huffman about kroto and smalley's C60

Alain Leger u paris stuies polycyclic aromatic hydrocarbons in dust clouds shows kratchmer the 85 C60 article

Kratchmer not to keen on idea, and busy with ESO infrared project

Huffman didn't think he could get funding, so got lamb working on semiconductors but told lamb to fiddle with it in spare time

87
theoreticians trying to approx absorption bands of C60

Larsson, volosov, Arne Rosen chalmers u of tech sweden publish CNDO/S calculations for buckyball for uv spec 340nm, 260, 240, 230 220

Huffman sends this to kratchmer and says, it is suggestive of the camel humps. kratchmer doubtful, these calculations are not accurate.

huffman gets idea that if his apparatus is producing C60, he should patent it  this gets him going

eaerly 88 lamb reproduces the 83 heidelberg results with new evaporator and got camel humps, but not very reproducible

gave up in feb

later aftert a conrference in july huffman convinced kratchmer to try again.  kratchmer got a neophyte undergrad student Bernd Wagner to do it. got irreproducible camel hjumps

THEN the student for the hell of it raised the pressure from 20torr to 100torr  AND this time kratchmer had access to high quality IR spec, the new samples had stronger camel humps but bamm 4 sharp lines in IR

geometry says C60 should have only 4 modes vibratioon

calculations run from 1429 1183 577 527 to 1655, 1374 551 491

kratchmer calculated from hight of his lines that they must have got 1%yield which seemed phenomenal  this blew the AP2 out of the water

lamb also eventually thot to raise pressure and got better camel humps but had no IR machine

Wagner went back to school vaguely aware that he had done something.

next comes grad student Konstantinos Fostiropoulos.  he and kratchmer checked forf every possible sorce of contaminants, couldn't find one.

by know the spectre of the cold fusion fiasco was making people wary of reporting hasty results...

couldn't riase yield or he didn't know if he could extract...

finally convo with huffman said, use C13 and see if you get the 4 lines to shift by predicted amount for heavier nucleii

C13 came in dust form, they tried various methods to get it into cylinders for the evaporator, not yet.  

conference season came around and they decided to report their results at the summer interstellar dust conference

mike jura attended and sent abstract to kroto...


summer 89
Kroto had tried this but didn't have enough equipment.  he couldn't beleive the reported yields.  decided he'd have to try again

he managed to get some sort of funding and student jonathan Hare  all these people are PHYSICS people not orgo chem! and simon Balm, balm left then amit sarkar, they got the 4 lines! but still weak and not robustly reproducible, then machine broke but they got funding to fix it


meanwhile fostiropoulos was trying all kinds of things to make the 13dust solid, was not supposed to be possible.  finally he got a lab to compress it under heat, and he built a new evaporator and by

feb 90
he got results, and measured the four lines they all shifted close to average .963, the predicted value was 0.9625, this was pretty damm convincing

***
at this point they are in contest kratchmer with kroto group, giving each other just enough info of results to show each other they are on the right track but not enough to show exactly how far ahead each is *****

mar90
Hare presented his 4lines at astro conference.  by now he was better at getting strong reproducible lines, distance of collector to carbon rods was crucial,,. by now people are more interested, a second repetition of very specific results, BUT STILL WHAT WAS THIS STUFF

[[BAR COULD YOU CONTINUE WORKING ON SUCH A PROJECT FOR 7 YEARS?]]

in between kroto asked hare and balm to analyse spectra from halley comet from giotto space craft [ALWAYS KEEPING FOOT IN REALITY OF OBSERVATION]  not bad idea as they now decided what they needed to do was keep reproducing the experiment and collecting soot so get big enough sample C60


mar90
francois diederich assoc of orville chapman and his group at ucla was working on long chain syntheses

they got C18CO6 synthesized then used laser desorption mass spectrometry to lift the molecules off of surface and gently heat off the CO to synthesise first ever C18 ring in sep 89

then they synthesized C24CO8 and C30CO10 these were 4 sided and 5 sided rings of 6 carbon carbyne groups, when they tried desorption of them, they got odd results

from C18CO6 they got signals of C18, 36, 50, 60, 70!
from C24 they got weak 24, but strong 48, 50, 60, strongest 70
from c30 they got NO C30 but huge C60, with following of 70

WHAT was happening?  they showed kroto, they didn't think they had buckyballs but kroto was worried they'd get large quqantities so back to work!


Hare took sample of soot tried NMR, MACHINE FAULTY! NO GOOD RESULT, went on holiday and gave some to grad student ala'a abdul sala, try mass spec:

got 60 and 70!!!! but then MASS SPEC MACHINE BROKE couldn't repeat!

SEEMS THE BRITTISH TEAM HAS THE CRAPPIEST EQUIPMENT AND FUDING!!!!


IN FEB 90 ebert and frenklach put article in chem engineering news comparing buckyball research to cold fusion!

6jul90
fostiropoulos and kretchmer publish their C12 and C13 results on camel humps and 4 IR lines shifted

then they noticed weaker lines and remembered C70 follows C60!

the race is on to isolate a sample of C60  but they were not chemists!!!

Kratchmer sends his C13 paper to Leger, who contacted Werner schmidt at polycyclic aromatic research group, schimdt tells kratchmer: try sublimate the C60 out of the soot around 800 900K in vacuo or i think C60 should be soluble in orgo solvent! don't use benzene poisonous

fostiro not being chemist tried sublimation, and got a sublimate!  put it in uv and bingo! camel humps without background of soot!  first to see uv spectrum of C60  he and kratchmer kept at it and got the IR spec

they sent to huffman, huffman and lamb repeated the results!

fostiro washed the slides with benzene, readily soluble so attempted to isolate more C60 with benzene in centrifuge, got deep red solution!  evaporated it and the dark powder still had the spec properties of C60!  they even watched crystals of 'fullerite' form under microscope!

now they had to do analytical work, again they are the wrong people to do it, not chemists, but they wanted to be the discoverers

first they did mass spec and got messy results.  HUH!

from crystals with help of werner kuhlbrand from nearby molec bio lab they got some poor electron diffraction patterns but at least gave characteristic spacing of one nm, this could be a match to calculated 0.7nm diam of C60 + 0.3nm thickness of graphene sheet

next they needed xray diffrac to show characteristic spacings of C atoms to show really buckyball struct


1987
Don Bethune, new phd student ucal berkely goes to IBM, hears smalley give lecture on bucky balls and watches...

1989
decides to try something new with that research.  he had no knowlege of astro community and didn't see kratchmer's Capri presentation.

may 1990
he and heinrich hunziker, Mattanjah de Vries, Gerard Meijer begin work, using laser desorption etc... device similar to AP2 but gentler lasers.  first they repeat the 1984 exon results.  but what new could they do?

bethune contacted Rohlfing from the exon group for ideas.  rohlfing joked just try to find it in carbon soot!  ibm teem thot well if its suppose to be so stable, why not?

they knew nothing of soot chem! so they made soot in the clumsiest of manners!  they put the soot in their laser desorption machine and got carbon clusters.  eventually they found burning plastic or acetylene gave good pure carbon clusters  but still too much contamination

19jun1990
so they went back for laser vaporization of graphite under 500torr argon and collect the soot 1cm away directly, bingo C60, 70 and higher signals, that easy.

at in house seminar july they decided they needed to do the C13 nmr to get the 1line signal.  but how much C60 would they need to collect?  they were gtetting better yeilds than had so far been publlished but still only 0.1 microgram.

Nino Yannoni suggests 0.1 to 1gram, get cracking then robert johnson says i can do it with 300micrograms but also ibm is big, they had raman spectroscopists even use scanning tunneling microscope on the film!

7aug
they published they preliminary work journal of chem physics


26jul
Hare reads kracchmers paper on C13 shift and realizes lets get going.  he remembers enough chem to try dissolve the soot sample in benzene.  sits like a lump soot not soluble [[WHAT IS SOOT]] goes home for weekend.  comes back: slight red color in solution!! filters off solids, evaporates adn deep red.  C60?

tries mass spec, machine still cranky BAD MACHINERY!


jun
huffman and lamb take fullerite sample and gtet xray diff: definitely new form of crystaline carbon but still need bigger crystals to get struct

they got big crystals.  dissapointment! xray diffract not clean signal.  this happens with cobolt.  maybe spheres pack disorderly, maybe C70 disrupts structure... damm

mention something vague about frostiro visiting another lab learning he could use chromatography to seperate hexane sol into bands, but doesn't follow up?  ***

then the lab people say: you should do nmr on C13, but he doen't understand importance of that either!

WOW, SO THESE RESEARCHERS ALL HAD HUGE GAPS IN THEIR KNOWLEGE OF WHOLE WEALTH OF ALL THE SCIENCE PARTS, EACH GROUP IS SEEING THIS PROJECT THROUGH PARTICULAR LENSES!

jul
huffman and kratchmer finally decided they had enough might as well publish but huffman wanted to renew patent!  green light they publish, phillip ball gets paper  7 aug

ball sent to kroto 10aug
kroto: damm they did it! now what?

kroto tells ball to send to bob curl as second ref

oddly huffman and kratchmer didn't have mass spec data!  their machine sucked.  so someone else ought to try.  kroto hare and abdul sala had mass spec before machine broke

Curl referee report: paper should include mass spec and NMR

***
OH: h AND k HAD MASS SPE RESULT THAT A COLLEGE MADE BUT DIDN'T INCLUDE IT CAUSE COLLEGUE WANTED NAME ON PAPER.  

WOW******



20aug
Bethune at Ibm is shown huffman etal july paper and lets get snapping, just do a makeshift graphite arc and collect soot and laser desorb it.  ok C60 signal  they even called huffman and huffman said we have paper in 10aug but no mass spec, go publish mass spec

so bethune et all send report to chem physical letters 24aug, smalley editor.

tyhen kept collecting soot till 20milligrams and tried sublimating C60 out, got it with C70


Kroto lab, they thot fast, consulted with chemists Roger Taylor and Jim Hansen and decided to put the stuff through alumina packed collumn in hexane. BINGO separated out 3 bands, with another lab's help, they got mass spectra one band C60, other C70, third mixed   FINALLY PURE SAMPLE OF C60!


end of aug
fuckit, Curl called huffman and said forget about my qualms, publish your paper!  they published with Zscheeg and Natuour's mass spec, they first send the preprints do many scientists


7sep
bethune et al publish raman spectrum with rosen and Tang, of sublimed C60/70 mix  the 273 cm^-1 line was most conclusive of squqashing/bouncing vibration of ball struct.  next they set to get nmr 1line


Smalley decided to get Kratchmer to a conference in germany to announce their C60 results 12Sep, meanwhile he gets HIS lab cracking on producing C60 using the Heidelberg techniques

[[RIGHT! SMALLEY AND KROTO SPLIT!  WHAT ****WAS**** THE SPLIT OVER?  MAYBE THAT KROTO GOT TOO FRIENDLY WITH THE GRAD STUDENTS AND IT WAS REALLY KROTO'S REL WITH THEM THAT GOT THE RESULTS?

ANYWAY THIS ISOLATED KROTO AND HE HAD LESS ACCESS TO PEOPLE AND MACHINES AND FUNDS?]]

***
ALL IN ALL THEY PUSHED EACH OTHER JUST ENOUGH TO KEEP THE BALL ROLLING!


>>>>
BUT DID THE SCIENCE NEED THEM TO ALL DO IT SO ****FAST**** DID THE CONTEST HELP ANYTHING IN THE LONG RUN?

IN ALL, THE PROCESS TOOK FROM 83 TO 90.  BUT IT HAD STARTS IN 60S  AND IT LANGUISHED FOR 25 YEARS WOULD YOU SAY ****THAT**** IS TOO SLOW?  ONCE THE CONNECTIONS STARTED HAPPENING IT ALL ZOOMED TOGETHER IN 5 YEARS REALLY.

BUT WAIT... THERE'S MORE IT'S NOT THAT IT WOULD HAVE TAKEN 25 YEARS BUT IT MIGHTA TAKEN WAY MORE THAN THAT, ONE PEICE AT A TIME WITH LONG GAPS... WITHOUT THE POSITIVE FEEDBACK FRENZY

SOME PIECES OF SCIENCE TAKE 150 YEARS.  ***THAT*** IS TOO SLOW.

Krotolab
Hare brings solutions to Gerry Lawless and Tony Avent to do NMR, they get the single line for the magenta solution! then the red solution, predicted 5 lines, some confusion, back to chromatography, almost misinterpret because one line is close to the hexane solvent line but finally yes conclusive: the 5 lines are what we expect for C70!  David Walter long time colleague of kroto convinced him this is the data that nails it.

3 sep now they get started on writing up results while Taylor kept at the chromotography to purify the C70 sample enough to get clean NMR 5 spikes.

kroto decides to visit kratchme4r to thank them for suggestions and show nmr results of separated 60/70

10sep
Taylor succeeds with nmr of purified 70 and they send paper to chemical communications jnl


3sep
Whetten meets Stace at a conference and stace tells him about fullerene results and whetten tells diederich.

11sep
not knowing how much work had already been going on, bethune reports on his work, preempting kratchmers talk the next day.  kratchmer urges him to publish the raman spectra

[[THE IBM LAB GOT IN LATE AND SUCCEEDED REALLY FAST BECAUSE OF ITS INTERDISCIPLINARY RESCOURCES!]]]

12sep
kratchmer gives his report  his photos of crystals and xray diffraction made audience realize something amazing in carbon science had happened

then smalley gave his talk on the original 85 work and La enclosed fullerenes

then whetten told group that he knew kroto had isolated 60 and 70 and got 1line nmr on 60 and 5 on 70

Whetten agrees to visit kratchmer lab maybe think ideas for better xray diffrac

smalley was amazed that the ibm team had been able to collect so much C60 from soot from laser evaporation where he and heath had spent year and gave up. [[did they have it all along?]]

15sep
bethune returns to usa and Meijer greets him at airport and rushes jetlagged bethune to the lab: photo of scanning tunneling micrograph of layer of buckyballs on gold surface! with a few c70s thrown in.  then also: the single line NMR spec.

WHAT YOU CAN DO WITH SINGLE INTERDISCIPLANRY LAB WITH LOTS OF MONEY AND GOOD MACHINERY!

BUT HERE IS THE DEAL, THIS IS WHY WE THINK OF C60 AS ***REAL*** SO MANY LABS FROM SO MANY ANGLES GET RESULTS THAT JIVE: mass spec, specific signal at 60 70, geometry, huckel theory, La in cages, suggestive uv spec, producing it from laser ablation and cooling, from carbon arc to soot, laser ablation... IR spec, tons of calculations from diff ideas, chem and sublimation purification, raman spec, NMR of 60 and of 70, crystalization, electron diffrac to get spheres, scanning tunneling microscope to get spheres...

AND AFTER 300 YEARS OF KNOWING HOW EASY IT IS TO BE FOOLED, THESE RESULTS ARE DONE OVER AND OVER AGAIN BY DIFF PEOPLE WITH SLIGHTLY DIFF TECHNIQUES  CO9NSTANTLY CHECKING EACH OTHER SO YOU KNOW YOU ARE NOT CHASING WILD GOOSE

ALSO TO REALISE THIS ISN'T SUCH AN ARTIFICIAL SPECIALIZED STATE OF MATTER BUT IT CAN FORM QUITE EASILY IN A NUMBER OF DIFFERENT ENVIRONS...

diederich and whetten work with Kratchmer to separate 60 from 70 publish some results in jnl phys chem oct 3
they were eventually able to get 14% yeild in their own carbon evaporator!!

smalley group built a fullerene generator with spring loaded carbon sticks that got 10% yield on 10 grams in a few hours!  they begin to do fullerene CHEMISTRY!

DEC 13
ibm stm image is published along with an image by jeffrey wragge chamberlin and white from fullerite obtranied ffrom kratchmer lab

STILL WANTED XRAY DIFFRAC to nail the carbon carbon distances and really show its buckyball

finally ibm gets solid nmr spec not make sense!  HOW DID THEY DEDUCE IT'S BECAUSE THE BALLS ARE ROTATING?  anyway by cooling the solid they get the spectrum to broaden as it should showing that the room temp balls ARE spinning, that's why no one could bet dcent xray diffrac nor did the stm image show any atomic detail, just fuzzy balls

the balls spin 10billion times a second, cool it enough and get ratchet phase balls click one atom at a time, till cool it to stillnes

at about the same time bell labs gets similar results

ibm then used C13 enriched cooled C60 to get interatomic distances.  two sets: 0.140 and 0.145nm the shorter distance in the pentagons, all together it makes the 0.71nm buckyball

bethune's colleage bob johnson then used another nmr technique to nail interatom distances in C70 that yield the 5 spike signal.  johnson's result also showed that the C13s are incorporated randomly into the ball suggesting that they are being incorporated into the ball during discharge in the gas phase atom by atom, not from peices of the graphite.

finally joel hawkins et al 91 pin some molecules to the bucky balls in the same places and get them to stop spinning and crystalize orderly, and get xray diffrac and get the two c-c distances: 0.1386, 0.14324  match!

buckyballs is a molecule!

Sunday, June 26, 2022

My Friend Asked Why Gold Is Found In Concentrated Deposits, Not Homogenously Mixed In All Rock

 

some scattered thoughts and notes.

 

gold
start with magma as homogenous as you want, as it cools, minerals start to separate out in Bowen's reaction series.  Gold and Silver do not have much affinity for entering these minerals, especially gold.  [why?]  the early minerals are dense and tend to settle in the cooling melt.  as more minerals form, the melt that is left becomes more and more volatile and silicate rich, i.e. water, sulfur, chlorine, and of course in gold and silver (copper).  eventually this fluid can get forced through cracks in the host rock and the gold and silver are dissolved in it.  as it cools in the cracks minerals like quartz crystalize out and the gold and silver (always an amalgam to varying proportions) come out of solution too.

I wonder if successive waves of water rich fluids can come through these cracks and either deposit more gold or dissolve the gold that is there and redeposit it, perhaps there are patterns that concentrate the gold further.

so gold ends up being concentrated in tight places and not finely mixed through all the rock.

as the host rock is lifted and weathered away, the gold does not weather or dissolve and since it is dense, gets concentrated further in placer deposits by streams.

so... is there an element as rare as gold that DOES mix higgledy piggledy with all the rock?


In general, the 96 elements on earth do not mix higgledy piggledy, homogenously, because, atoms are particular, responsive to each other, and mathematics gives a complex discrete but finite set of solutions to systems with constraints.  you dont get a higgledy piggledy mix of regular polygons when you try to fit them together around a sphere, you only get 5 possible solutions.

ditto with atoms.  they only fit together in a discrete number of ways.  naively you might think that the number of ways to combine 2 dozen kinds of atoms into groups of 3 to 5 might be (ignoring geometry) something on the order of 24^3 to 24^5, which is 13,000 to 8million.  tho why stop at 5? why can't all 24 kinds of atoms mix together? now we are talking about astronomical numbers of combinations! at any rate, we've found only about 4000 kinds of minerals so far!  so mathematics and physics limits the number of solutions.

after that there are other properties of minerals to consider: solubility, density, melting point.  these can further separate things, so that the 4000 minerals aren't all mixed with each other higgledy piggledy.

then there are dynamic processes, iterating rounds of processes can again separate minerals out and concentrate them.  there is the basic processes of magmatic differentiation which ultimately creates continents of different mineral composition than ocean crust.

**
further note: in early formation of earth, accretion and radiogenic heating melts dense iron nickel, that sinks to center,

i suppose next up is olivines, in fact, as earth material begins to melt, olivines are still solid and dense and will also sink?

ok... i want melting points of minerals but u got eutectics and so melting points depend on what other minerals are also present, complicated! oh yeah also pressure.

anyway, other minerals tend to collect closer to surface

but hotter earth... will have even more convection... so that will add a dynamic.

so (Q) how will temperatures begim to evolve as a function of time AND depth?  there will be feedbacks, as differentitation occurs, radioactives will collect in mantle and crust, and even if hotter at depth... more pressure, so melting points will rise...

what if we ignore accretion heating, start with homogenous sphere.  radioactive heating begins.  cools fastest at surface, so heat accumulates towards center,



In addition, some heavy metals such as gold,
lead, and uranium, which have low melting points or
were highly soluble in the ascending molten masses, were
scavenged from Earth’s interior and concentrated in the
developing crust. This early period of chemical differ-




NOTES
gold alwys found mixed with silver.  completely solid solution

notes from earth maerials: min and petr

chapt 16 economic mimerals fr veins and pegmatites

pg 1450

from geo text:

magmatic differentiation:

basalt cools: heavy minerals settle to bottom.  some metals: chromite, with other metals in Montana's stillwater complex or Bushveld complex in south africa with 70% worlds platinum.

Pegmatites:
granitic, dissolves heavy metals
water and volatiles do not crystalize with bulk
left for last stages
these stages fluid rich, ion migration enhanced, grows BIG crystals. cms to meters.  pegmatites

feldspar xtals as big as houses, muscovites meters across, spodumene in the black hills as large as telephone poles!

also contain rare elements (Q WHY?) lithium, cesium, uranium, rare earths, beryl topas, tourmaline.

most pegs occur in large ig masses or dikes veins cut into host rock

not always granite.  Kiruna Sweden has magma with 60% magnetite solidified.  largest iron deposit



HYDROTHERMAL DEPOSITS
chemically alter host rock so called hydrothermal metamorphism, chapter 8

late stages of magmatic processs at top of magma chambers, leaves fluids, metals dissolve in it, and volatiles like sulfur, it moves thru cracks and as it cools precipitates sulfides, quartz,  and native metals.

can produce copper deposits like michigan


Dissemination Deposits
not concentrated in veins dikes, distributed as minute masses thruout entire rock.  WHAT MAKES DIFFERENCE? much of worlds copper is foudd like this.  very UNCONCENTRATED.  bad mines.  WHY COPPER DO THIS AND GOLD NOT?


HYDROTHERMAL METAMORPHISM
229 284

low pressure variety from groundwater seeping down and being heated and dissolving minerals as it goes.

high pressure variety deeper is from fluids from late stages of magmatic cooling, at tops of batholiths it seeps thru porous host rock or cracks.


third enviornment is ocean floor near mid ocean ridges.  fresh hot magma below as it cools forms a convection system of ocean water seeping into cracks and flowing down, heating, and being expelled when hot, bringing more cool water in. these hot fluids

serpentinize the mafic minerals in the crust, releasing H2 and oxidized Fe, Mg ions, Leaves serpentinite and soapstone.

and also dissolves metals such as iron, cobalt, nickel silver copper gold!  as the fluids rise to the ocean, they cool and precipitate black smokers depositing metal rich sulfides and carbonates.

OK: how localized are these fields?  what is their fate?  as the ocean floor spreads...   FIRST OF ALL, THEY GET BURRIED UNDER SEDIMENT OVER 10S OF MILLIONS OF YEARS, 100S.  THEN THEY GET SUBDUCTED!

geologists think the copper deposits in cyprus come from these.  LOOK IT UP.


MELTING
lets explore this melting thing.  if you have a solid mineral assemblage, n minerals, they will share faces in pairs, edges in pairs or triples (or more i guess) and vertices with triples or quadrupals etc... i suppose the more minerals mixed the lower the eutectic temp?  so as you raise the temp... the vertices will melt first!  that's VERY little volume.  then each different edge will begin melting depending on the combination of minerals i.e. if there are 3 at once..  last to melt will be faces.  but not really.  depends on teh eutictic temps of each combination we have.  some double eutectics might be lower than some triples?

at any rate if it's slow enough... the crystals will slowly melt and settle as the melt rises.  as we reach the eutectic temp, the melt
will be at eutectic composition and temp will not rise, as heat goes into melting, untill the entire fluid is at the eutectic composition.  if heating stops here, the magma will be at that composition and rise to cool somewhere.  

so most igneus rocks are similar compositions because of eutectic points!

differing compositions will come from higher temperature melts!


melting points
0    water
100    water boils
112    sulfur
444    sulfur boils
800    min temp of SiO2/H2O melting high pressure
1500    various forms of SiO2
1700    various forms of SiO2
3000    graphite/diamond
4000    graphite/diamond

Thursday, February 24, 2022

You Too Can Explore A Real Asteroid!

So here is the database for the curation of the pebbles/grains/dust that Japan's Hayabusa2 space craft BROUGHT BACK under hermetically sealed conditions from asteroid Ryugu last year.

https://darts.isas.jaxa.jp/curation/hayabusa2/

 


 




you can download a pic of each under magnification.  also it seems you can borrow them?  god knows what kind of qualifications you need for that, but researchers obviously borrow them to study, maybe make microslices and analyse them.

it begins.  they look like some kind of slaggy crumbly dusty coal.  they may be of similar structure, though not from biology but from interstellar processes and early solar system processes.  they also look like they WOULD NOT survive entry into our atmosphere as meteorites (even if they were larger peices)  my gut tells me we don't have meteorties like these.  But I need to look up what we've learned about them so far.

Basically this is stuff left over trom the origins of the solar system.  These things formed maybe near the asteroid belt.  Closer in... pebbles formed with more rock and iron (like earth).  Further out things formed with more ices (water, methane, carbon dioxide, ammonia...)  But there was much mixing and then more mixing and processing quickly after formation.  Japan and I think NASA has previously only brought back a tiny bit of DUST particles from an asteroid or comet.

Of course we have brought back many pounds of moon rock, but they are rock and geologicaly processed, not from the beginings of the solar system.  We also have tons of meteorites of many types of origins, but the delicate ones like Ryugu stuff, is very altered by its passage through our atmosphere.  We also have a couple dozen chunks of rock that got splashed off of mars by big meteorites hitting mars, and landed here as meteorites.  except for one, they are all young and heavily processed by mars geology.  We also have

i remember when hayabusa2 sent bouncing robots to explore the asteroid's surface they decided that the rocks they were bouncing on were NOT very strong.

https://en.wikipedia.org/wiki/162173_Ryugu

 In a few years,  NASA's Osiris Rex will return more samples (perhaps more and larger than these) from a similar asteroid it also visited, called Bennu. I don't know why O-Rex is taking longer!


If I had the presence these days... I'd write REAMS about this stuff.  Actually... I'd learn more too.

Thursday, February 17, 2022

Why Do I Do Natural History? (my 3rd exercise, one night, when I had to teach myself to write an essay for an exam)

Each year I try to learn about a group of plants or animals that I haven't learned much about yet.  Last year it was aquatic plants, this year it's spiders.  

What I do is I get some books about the group, about how they live, how to find them, and some technical field guides which tell me how to identify them to species.  The latter part is often difficult and requires using tools like a dissecting kit, and microscope or at least hand lens and developing odd technical skills.  

Then I go outside and find, observe and (sometimes catch) and analyze the critters.  Why, you may ask, do I go through this each year?  It is not my profession!  Well, there are intellectual, aesthetic and ultimately spiritual reasons.


One of my main intellectual interests in life is how the universe keeps evolving to more and more complex forms.  I may even go back to school and study the mathematics and physics of this.  

Differentiating between this species and that, often involves counting and noting the positions of spines or looking at microscopic features of the beasts.  That activity really puts me in touch with how complex they really are and keeps me asking "How?".  "How does simple chemistry become living cells that can produce all these hairs?  How do all those cells arrange themselves to make a jumping spider that can find and catch another insect?"


The easy reason why I do this of course is that these plants and animals are absolutely beautiful once you take the time to look at them.  Jumping spiders?  those big puppy eyes and furry paws they have!  And then the sheer delight at watching one stalk and pounce on its prey.  

On a larger scale, the more kinds of plants and animals I learn to see, the more richly textured I see my landscape.  At one time I knew over 500 different kinds of plants in my state and at first I thought this level of analyticity would destroy my gestalt sense of beauty, every time I took a walk, recognizing this plant, that plant, hundreds... but in the end, it just increased the depth of the texture of what I saw.

And then knowing how each critter lives helps me see how interconnected that dense texture is, how it functions like an organism itself.  This to me is beautiful.


Finally, I don't go to exotic lands to do this, I find these critters in my own landscape, around my house, in a seemingly ordinary crack in the sidewalk, or within walking distance or a bike ride.  It helps me feel connected to where I live.  It helps me feel that my home is alive.  And that it is wild, not concerned with the petty human rat race.  

When I get down with that jumping spider and watch it closely enough to count whether there are two or three pairs of spines on the "ventral side of its front metatarsi...", and begin to imagine how he uses them to capture his prey... and I've lost myself for an hour.  

I really immerse myself in the wild landscape and forget this petty human drama.  Ultimately in my natural history excursions I loose myself and become whole.

Thursday, December 30, 2021

NASA so far succeeding in horrendously complex process of unfolding their new telescope in space

 I think there are 600 discrete steps or so.  it's a monstrous thing and had to be so folded up tightly into the rocket to get up there... i'm outside so my hands might be too cold to type in a description.

here is photo of the 5 sunshields unfolded for testing, messy delicate
https://bestgamingpro.com/james-webb-space-telescope-unfolds-its-sunshield-in-test/



here is photo of 18 segment primary mirror and secondary focus mirror way up there all unfolded
https://www.sciencealert.com/nasa-just-unveiled-the-james-webb-space-telescope-s-huge-golden-mirror



i dont think theyve ever had EVERYTHING unfolded at once

here it is all folded up for putting into space capsule



here is animation of unfolding sequence
https://www.youtube.com/watch?v=6RcMfAAiGFI

here is NASA webpage showing what stage of unfolding we are at currently
https://webb.nasa.gov/content/webbLaunch/deploymentExplorer.html

we are at step 12!

this nasa we blog keeps us up to date

https://blogs.nasa.gov/webb/

then we have to get to it's orbital position and then we have to wait months for it to get really cold!  it needs to get cold because it is not a visible light telescope, it sees in infrared (radiant heat, subtle radiant heat from billion light years away galaxies.)  so just like you gotta keep stray light away fromm telescope at night, we gotta keep stray heat away from james webb telescope.  so we cool it to 100s degrees below zero and shade it from sun AND earth. that's what the 5 sunsheilds are for.

what will we see?  galaxies way way close to the begining of the universe.  star formation, and ATMOSPHERIC CHEMISTRY of planets around OTHER stars!  and things we haven't yet dreamed of.

good luck

 



Thursday, October 28, 2021

Beavers at Fitzgerald Pond

 
after trying to get him to splash, i figured out that he'd do it if i clucked at him.  curious bloke he kept coming closer to look at me.  I think there is a family of them.  of course i forgot to take a picture of their lodge.  maybe today.



 

Tuesday, August 24, 2021

Finally Looked Up A Cool New Lichen I Found: Lecanora thysanophora

 Ok i finally looked up a lichen i found a few months ago in the woods on the way to arcadia park off the bike trail to easthampton ma.


Lecanora thysanophora, cool structure, i should get it under the scope and see what on earth it is doing. watching it grow wld be cool too.

I don't know why it grows that outer band of white fibers. the mealy center portion is where it comes apart in tiny bits to blow around to new tree trunks to grow on. These guys don't seem to be having any sex. I think this species rarely does.  Many lichens DO have sex.  In the pics of species from waysofenlichenment you see many with rimmed dots.  those are where two separate fungi critters are intertwined, having sex and making spores to blow off in the wind.


Remember, being a lichen, this critter isn't eating the bark or digging into the tree, it's just resting there letting it's internal captured single celled algae (Trebouxia) grow food for it from the air and sunlight.
 
Lecanora is a rather diverse genus, you have no doubt seen it. grows on wood and rock and stone walls.
 
(my photos)
 
 









https://www.waysofenlichenment.net/lichens/Lecanora/
 
oh by the way... those reddish crisscrossy veins... are a liverwort. i should make a post for them too eh? Frulliana species. here's some from underneath under the microscope. 



and here's a pic of one of their fruiting bodies springing out spores with their springy thingies.