Document QLLoZbGMvxndg1mO7xBbwvYL
E. I. DU PONT DE NEMOURS & COMPANY 256 VANDERPOOL STREET NEWARK, NEW JERSEY
NUMERICAL FILE
NEWARK PLANT PIGMENT COLOR RESEARCH REPORT
Period Covered
joss 19& * 199* mm TUB)
FILE,
DATE*
HJ 4497
$
!
co>a<jvvn*PtJW-*
Serial No. KN-54-18 Copy No. i
Copy foi - Numerical File * Research Office (210) * Library Hie (210) * P. J. Monahan (X files) * J, N. Tully/A. Siegel * W. F. Spengeman/Library * Extra - Extra
NEWARK PLANT CHEMICAL DIVISION - COLORS
Progress Report*
AA-33-C * FERRIC PYROPHOSPHATE
mm 1950 - JUNE 1954 (PART TIME)
CHARGE} 1101-11-182 1101-11-277
?/i/n
DATE SUBMITTED* 6/28/54
DATE ISSUED*
7/8/54
DUP050069836
mmmnm
This report summarizes the status of work done on ferric pyrophosphate (AA-33-D) as a candidate pigment for the fortification of supported organic polymers and plastics such as alkyd and lacquer systems*
For a general discussion of the tread objectives of this study^aig^lta relationship to other pigments under study at the timef
This pigment is also trader study as % flame retardent for cellulose acetate (see KN-5h~l6). Potential applications in un supported plasties are discussed in KH-54-15.
Despite the ineompletion of certain of these studies, this report is being written at this time because of the transfer of the writer to other work.
1* This material is a good film fortifier for alkyd and
lacquer systems* The major deficiency of the product in its present
form (SW-1567, 1570) after approximately
9ismoanthtesnFdeloncriydatot*5de8veeloxppoasuhreeaivny
bronze alkyd.
in alkyd end
lacquer paint systems. Color retention, polish back, and film
integrity are all excellent.
2. A coprecipitated 50 mol % Mn/50 mol % Fe pyrophosphate
(under evaluation In Series 10399 * KBf-5**17) is shoving excellent durability properties at 9 months exposure* Improvement of gloss
retention in this product would be of definite interest*
3* AA-33-D (SW-1567) la its present for* is inferior in gloss retention to other candidate film fortifiers such as A43*t*D TiaMh*19) or AA-36-D (KH-5^-lh), in alkyd systems* In other durability characteristics it is comparable or superior, and possesses the advantage of lover Initial color and greater trans parency versus these candidate pigments*
V* M-33-D le superior to
M> as a film fortifier for
lacquer systems. Comparisons with AA-36-D seem to show an advantage
for AA-36-D at 6 months exposure (8-10*10)
5* The relatively low cost of AA-33-D raid its soft texture make it a very attractive dry film fortifier candidate*
DUP050069837
ft* following exposure programs are under way and should t* completed*
10343 10346
10399
10400 1C402 10405 1C407
10410
1042? 10429 10433
COMPOSITION
Mstallies Blue Trim Paint
SW-1567 SW-1570
Clears-Hetallies SW-1567
dip
Clear vehicle, AA-22-D Clear, A-6-B* 01-734* AA-22-D, AA-34-D, F-f-D,
Metallies Metalllcs Clears, Metalllcs Betallies
SW-1567, 1570 SW-1567 SW-1567 sw-1567, 1570
ar, GX-734-D ar, AA-34-D, F-4-P
Metalllcs
Cleara-Metallies Clears-Metallica Neoprene Stock
SW-1567, 1570
1470-17, SW-1567 1470-22,23,24,29 SW-1567A570
Clear, A-6-D, AA-34-0, AA-35D AA-36-D.
Clear, sw-1567
Clear, SW-1567
AA-22-B, Basle Aluminum Sulfate,
In addition to these studies current activities on the flame retardeney of cellulose acetate and fortification in unsupported polymers should he completed. (see attached list# of samples submitted to various individuals)*
Samples under evaluation by various groups,
SW-1567
imm,,
*1*
sw-1567 SW-1567 SW-1567
JJ - Bannerman, Textile)
JJ * Lantos
Fibers )
B.H.Zabel - Lusena
4/27/54 6/1/54
4/6^-
*
Various samples to Textile Fibers, Waynesboro KN-54-16
Cellulose Acetate Flame Retardeney
DUP050069838
-3 -
flaanle Ho.
Reference
m
1*99 1567 1570 1567A570
G*W* - R.E.Pike, fay
JJ * wa - Newport
GW * H.G.Swanson, Pdf
sw -
ray
JJ - S.C.Horning, FdF
1/30/53
Thtmcw mm*
Paint applleation
v/30/n 6/29/53
M
11/24/53
M
n
m m
n
Attempts to modify the glees retention characteristics of this pigment in alkyd eyeteas ere under evaluation in Sxposure Series iWf and 16429* Improvement of gloss retention in alkyd should make this product of considerable interest to the paint trade* Present durability characteristics of the pigment in lacquer systems are of interest to fw.
<p .t *s *b *#34 m> 6a M),
She potential uses in paint systems would involve such appli cations as -
1* Durable highly transparent clears*
2* Durable neutral grey metallic finishes when blended with aluminum*
3* Blending agent to give durable combinations with more highly colored and more expensive pigments*
The outcome of these studios should permit a decision as to the potential applications for this type product*
DSH-53-4 DSH-54-7
DSP-54-8
AA-33-D Effects of transparent extenders on unsuooorted uolvasrs* Effect of AA-33-D on flammability of cellulose acetate*
eculative Inorganic Studies* -33-D in Cellulose Acetate* AA-33-D in unsupported Polymers. Belated studies on inorganic film fortifiers*
Inorganic croup, June 1m * June *91**!
DUP050069839
-4 -
Ho investigation of the patentability of the application of AA-33-D as a film fortifier for supported polymers (paints) or unsupported polymers has been made*
A patent proposal on the use of AA-33-D as a flame retardent, has been written (JJ - o/23/Jr* - Metallic Pyrophosphates)
A survey of the literature concerning the chemistry of the ferric pyrophosphates has been made (JJ - Memo for file - 1/29/54) and a copy thereof is attached to this report* Patents on substances of related compositions that have been reviewed include * 0*S.2,227,928, 0.8*2,357,069.
The first experiment on AA-33-D is recorded in HB 1376*18 (JJ - dated 7/L2/50). The product was revealed to others in the inorganic Laboratory Monthly Summary of August 7, 1950, and in exposure program 10284 dated 12/20/51. No samples have been submitted outside the Company as of this date*
romMimidi This product has been manufactured in the laboratory and
in the semi-works without difficulty according to the following equation -
3Fe2(SQl|.)3 + 3Ha^J*20p --4 (feif^^O^Jjj^Nai^PgOyJy (HgO)^ HagSO^
The composition of the products obtained has been shown
to vary with the
ratio used at the strike.
(See summary in Memo by JJ - 1/29/54) "Chemistry of Ferric Pyrophosphate Literature Review", which is attached to this report* Typical analytical data are given in this report*
The products obtained in the laboratory and semi-works have been examined by electron microscopy and x-ray techniques. The material is approximately .1 - *2 micron in site and amorphous
to X-rays* (IB 1444-7 - Fils 210*2),
The specific gravities of the semi-works lots are 1567 - 2.07, 1570 - 2*04.
DUP050069840
IABltE.,.1
-*-
TESTED IN
muimm
1376-18D 10284, 6 1415-75 10340
l4i5-77 10340
141^-78
1415-79
1415-81
1415-83 1446-3 1446-4 1446-57
1470-12 1470-14 1470-15
10344
10400 10402
1470-17 10427 1470-22 10429
1470-23 10429
1470-28
1470-29
1470-36 1470-45 1470-46
S.W.1567 1570
10340 10340
1738 10427 1739
-...mmmjnmm.
COMMEHTB
Original process
pH, beat development Reverse strike
Coprepipitated with
PgOy-^/OH-
- poor gloss Heat development confers better gloss retention
damrkderurcaobloilristy-
Souroes of Fe*^, pH, volumes
approx, equal process.
to
FeClJ*
B-216-D - AA-33-D
RT-525-D - AA-33-D RT-647-D - AA-33-D B-63-D - AA-33-D
+ * color retention, gloss retention, flln integrity, , less browsing. greater transparency - . poorer light-fastness.
better color stability,
better texture,
F-5-D - AA-33-D
better texture,
tike 1415-780
*^/F207Jt ratios
used as a pulp color.
No advantage over dry pigment
change in composition & yield
n
Effect of Mg & Mn In copperas
Fe+3/P2o7-4 ratio
darker colored products* result from higher impurities
change in composition & yield
AA-33-D treated with Fe, Fb, Ca, Mn
flame retardeney studies
AA-33-D treated with Hyponate, Arquad S, Naphthenic Add, Silicone
AA-33-B - effects of Al, Sb, Ti
AA-33-D - use of N3H.F&O7
under evaluation
AA-33-D - use of Sb,Ti flame retardenoy studies
AA-33P> - use of H
tt
en
AA-33-D - use of Sbffi
Repeat l4l5-78C -type
nn
Study Fe*|3/Pg07Jfrati
H If
it
If s
ft
good reproducibility and duplication of lab* process under evaluation
DUP050069841
TABLE II
HORSING COBFBRBWCB - HAY 3.
AU. PAHBLS FLORIDA BUPOSPHB VS6 0HLB38 OIHERWIBB HOTBD
AA-^-D - BASIC HICKEL CAHBOHATE
S-10262 12 Mbs, Florida. Dulux 448/3078# 1*3 P/B =* ,25 Mas stone.
#1 Flushed Polymer K, lot 10271.
#f Dry moEU
#6 AA-34-D - I376-78C. I Ni s 1 CO3
S~10268 * 12 Mos, Florida, Dulux 448/3078.
#1 Clear
#11 AA-34-D - l4l5~9C, 1 Ki * 2 CO*
#16 Polymer K ~ 10271
J
1*3 P/B ,35 Masstone,
>
S-10278 - 12 MOS. Florida MS
18 Mos, H.J, 45S
Syntax 23/60 1*1 F-19-A. Clear F-15-A AA~34~D F-16-A Dry Ii(OH)
F-18-A Blanc Fixe F-17-A AA-34-D
J-19-B J-17-B
24 Mos, N*J0 S.F. J-19-C J--17-C
Dulux RC 448~3078 1*2 F-39-A Clear F-38-A Poly K P/B ,16
Bakellte W-1251 F-aS-A Clear F-26-A AXtOH)% P/B * ,20
J-39-B J-3S-B
AA-22-D *84 P/B
Poly K 3^ P/B
J-39-C J-29-C J-33-C J-38-C
J-28-B J-26-B
J-H28-C J~26"C
DUP050069842
<m 2
8-10325 - 9 Mos, Florida. Dulux P/B = .35
#2 Polymer K - 10271 #9 Clear #10 M-34-D - l4l5~61A Isl Mi/CO*
5$ Reynolds LN-37
S-10326 * 12 Mos. Florida. Syntez 26/Resiisae 881 90/10 P/B * ,35
#L Clear
Masstone.
#2-3 AA-34-D 1415-61A lsl tfi/CO^
AA-33-P (Fe^(P^0y)^(grailP207)y<H20)^)
S-10284- 6 Mos. * 12 Mos, Florida Syntez 26/Resimene 881,
P/B -- .35
Masstones
#1 Clear
J Blanc Fixe
AA-33-D ~ 1376-18D
A&-34-D - 1415-9A lsl Mi/CC^
90AO
As above.
Clear + A1 Blanc Fim
5% Reynolds LN-37
S-10340 12 Mos, Florida.
#1 Clear #11 SVML567 #12 SW-1570 #19 Midas Gold 2344
Syntez 26/Resimm 881,
90AO PA = .25 5$ Reynolds LN-37
DUP050069843
3
S~10402 - 6 Kos. Florida. F-4-P.
#If1r
Clear AA-33-D
-
1567
Dry
#6 M-3*+~D - 1690 Dry
#8 F-M--P
Two-roll lacquer.
4-.5# Pigment 55 Alfcron #1570
S-ldM-05 - 6 Mos. Florida. Syntax 26/Besimene 881. P/B
5 A1
#1 Clear #2 AA-33-D . 1567 m AA-33-D 1567-1570 #15 AA-3S-D 1690-1707 #+ M-S^-D 1690 #13 AA-S^-D 1690-1707 #19 Polymer K 50303 #7 Clear + A1
#8 SW-1567 #18 SW-1567-1570
#16 AA~3*M> 1690-1707 #10 AA-3^-D 1690 #1** AA-3^0 1690-1707 #20 Polymer K
?
.25 .15 .35 .25 -- .15 --
.15 ----
.25 .15
35
ll5
.25 5
.15 5
.15 5
AA-36-D 85 Or43 15 Fe*3 <QH),
S-10^4-2 - 12 Mos. Florida. *u***,~
#2 AA-36-D #3 A-6-D
Syntax 26/Besimeae 88l.
90A0 P/B .25 % Reynolds LN-37
DUP050069844
mmlit 3*M3SIIm,M
3-10^2
*& & $$***
(See above)
Con0 trol
GT-674--D
n
mn
nn
ft n
n ti
11 tt
YT-562-B
nn
It
Mn
tt n
II n
ft n
P/B sis .06
n
n
it
tt
it
tt
P/B
ss It
,06
n
It
R
tt
+ AA-36-D P/B + A-6-D + M-3^D + M.G.2344+ AA-33-D + Blanc Fixe
n.20 it tt tt it
SB '5?
Total
8= w
tt
as: tt
s= w
P/B it tt 11 it
.26
+ AA-36-D + A-6-D + AA-34--D
P/B
.20
'm S3
Total
n
P/Btt
.26
n it n
+ M.G.2344-
tt = R
+ AA-33-D
tt SB ft
ft
+ Blanc Fixe w SB it
n
as w
- 12 Mbs. Florida - Syntax 26/Resimene 881
HT-6M-7 tt
tt
" P/B 04-25 P/B .085 P/B .085
+ AA-33-D P/B ,1275 + M-33-D P/B .085 * + AA-33-D P/B -085 -
m tJL
.17 3 .085 3 . 04-25 3 .17 .75 .17 1.50 .17 1.50
On Toney Basis
Wet blend Dry Mend
DUP050069845
*5-
12 Hos Florida 4-5S. Syatesc *K>
#1 50/50 #2
*3 #? #8 #10
BP~173~D/R6lO
n
R i
+ AA-33-D + Snyfox
n 4"
6 PVO * Total
6 PVC 6 PVC
10
h6
10 10
10
DUP050069846
*6 -
Other Iron phosphates that have heap examined include -
te^PftPa -SB1376-18
P2P27 FePOij,
*m -HB
"
Fe^(P^ 1470-24
(See Exposure Series 10429)
1AM STATUS >
A review of the status of transparent film fortifiers for paint systems was held with Pr* S. C. Horning of the F&F Department on 5/3/54 at Newark. Typical exposure panels* available at that timef covering AA-33-D and AA-34-D were shown* This information is summarised in the attached Table ZZ and in an Office Trade Heport of 0* Wormald dated 5/3/54*
DUP050069847
8 Weeks
SHELF
FIGMENT ggsraW IN IT IA L SHELF 120F SHELF 1 2 0 ? SHELF 120<>F SHELF 120F
V Weeks
seconds.
v is c o s ity .
3 Weeks
Cup I n
h ig h e r
DATA Off BEACTIVITT PAINT SYSTEMSg
2 Weeks
r -d
Fo
ber
eading # t
igher num
89
as
sift
33
30 30
coco HH
COH MfO
ii
11I
*
89
oo> MH
SISK
103 100
NN (MM
COCO HH
ss
c*o as?
ii
88
O C> MH
?
g&
<S3&
VsVs MM sid
QOOs HH <Jv MR
S*
8R HH Us
99
*$$ rlrlrt
l 99
9 99 4 H
VMft
99
1
? **
fa
S c>p
1 MM
1
B i u>us
CO
I U\ &m
S2 ' 23
?
*4 a
*
u\ \M0 jSt rj'St 1
* VD
m . * g(nSrRuRo 9 H 1 g W
s?~
o
1*1. . *3
rS2
|0>
Hfa*M*' s3 i5d?
ISO
&&
rlrf
JNQ
&&
HH
INO
&&
HH
0*0 HH
C*OO0S
999
rirtH
1 Week
H
H
F/B = ,15
42# s o lid s
TABLE I H
DUP050069848
11 aa
4 si
%F\ U> 11
Vn h fO CM
* *
e ft
aa
a si *
UN WV\ VN 11 UN UN CM CM
88
aa a
i
On
1
W V\ H IfN
I
8
S
DUP050069849
DUP050069850
c.c, J. N. Tully/A. Siegel A* Jo Stratton B. H. Perkins J, Jackson (2)
wuammjsa^nuL^
fiBMsPK
NEWARK, NEW JERSEY Jan u ar y 29, 19*.'
mm
This survey was undertaken to determine the possibility of claiming M-33-D as a new composition of matter in a proposed patent.
The reactions between ferric ions and pyrophosphate ions have been studied quite comprehensively. Pahl (1) (2)e
Pahl (1) Kung Svensk Vat Akad Handl Offers 3St 7> 37 (1873) (2) Berichte A 146? (1873)
States that ferric pyrophosphate is soluble in excess of pyrophosphate to yield, solid solutions of varying composition:
Felv(P207>3 + 5 Vb^27
FV p27 )3 * <N^.P27 }5
Pe4(P207)3 .2 Na^P207--5 Falf<P207)3e(Na^P27)2
More recently, Rodgers and Reynolds(3) have studied these
(3) Rodgers and Reynolds J.A.C.S. 2k 2081 (19^9)
reactions by conductimetric polagraphle, and potentiometrie means* These workers have concluded that three inflections in the curves result when .1H metal solutions are titrated with pyrophosphate until precipitation occurs. Similar results were obtained by a reverse titration. These inflections occur at
1st .5
2nd .96 3rd 1.33
1 Pa0?]'1 Fe^.(P207)3
DUP050069851
Bauerand Mte <4} report .ftM 1^07)3 3,8 sol'1^1 ia
(4) Bamt$@ ana Mltra Selene and Culture M 530 <1951) C.a . h& S5 <t?53)
excess sodium pyrophosphate and In the main substantiate the above
findings. These sorters also stalled transport experiments and showed the presence of iron in the anode chamber (negatively charged particle), and absence of phosphorus in the cathode chamber (absence in positively charged particle). These studies substantiate the existence of the above mentioned ions*
Our studies of M*~33~D precipitation conditions reveal
that yields and sodium content increase simultgneet&ly with an
increase in the
present at the time of precipitation:
M~33D Composition of Solids Dried at l4oF.
igm Fe^CPgO^)^,? HgO (Theory)
226,8
iJl
1470-12A 1SB 12C
12D 12E
1*64
is.70 l*,7l4 (AA-33-D Std,
Ratio)
li:W
240 240 246 246 248
St ,88
1,30
14a 1 s ,79 14b ls.827 14C Is.865 14d is.902
1,00
1,46
1,76
2.30
16A Is .64 16B Is.714 16C ls,77 16D is.827 16B is.907
Variations are probably due to differences in moisture in various series.
These results may he explained on the assumption that a
solid phase containing sodium pyrophosphate is being formed, and that this phase is not increasing in solubility with increased sodium content. The composition of the solid phase isolated at approximate stoleheometrie ratios of Ingredients cannot be quantitatively determined from existing data.
DUP050069852
3
Typical analyses follows
Code
Lot $ MpO
Loss on % Ha % Fe % P2o5 % s%
(Toluene) Ignition
AA-33-D 1567
22,0
29*8
1.9 20.63 40*86 *18
AA*33*P 1570
21.8
27,8
1.4 21,83 41*42 35
The sodium content of these products is far too high to he explained as being present as sodium sulfate*
Indirect analysis calculations hare been made on two bases $
(1) Solid phase is Ha^PgQy P|MP2%>3 V
Calculation based on F and Na analysis*
(2) Solid phase is Na Fe PgOy
%0
Calculation based on 'Ha sM HgQ analysis
Results of these calculations are tabulated below*
Premise (13 F%(P27^3
1567 1570
68. 72.
$ Ns^.PgOy 3*56
% HgO
Call* 25.86 23.64
HgO Toluene Dlstln.
^Xf6waT
22*0$ 21*8
Loss on Ignition
29.8 27.8
Premise (2)
$ F%<P207>3
1567 1570
64*6
$ IffaFePgOy
.20
13.
$ BgQ 22-
# Fe calc*
21*9 22*3
Up % Fe Found 44*4 20 44*6 21
fos&d? 40*86 41*42
The latter calculations are not in as good agreement with the observed analysis, as the former*
DUP050069853
These results lead to the conclusion that the product obtained at approximately stoicheometric ratios of Fe/PoOj (see Table E) is essentially a solid solution of ftajjVCU.lO BLO in Feji.<P209^ 9%0* This,in the writer's opinion, can'he predicted from a study of the literstore and the composition is not novel* Some argument might he proposed as to why the compound contains sodium instead of being a normal ferric salt* Since these pre cipitates are amorphous, adsorption of sodium ions might explain their presence*
We have currently under study the question of composition of the solid phase versus utility of the pigment as a film fortifier* Based on earlier studies of AA-22-D, the writer does not believe that products containing higher sodium contents will he superior to the existing formulationf but tests are under way to determine if this is true*
In the writer's opinion, based on the information at hand, the basis of a patent for AA-33-B should be a "use" patent similar to the proposal on Polymer K
JJ:MPH
DUP050069854
v r^Ut:
'-*`1
a* % A*; -
*
>
A#
*
DUP050069855