Phosphate binders, particularly acidic phosphates of Al and Cr, are used for binding Al silicate refractories used for lining of burners, SiC refractories, and refractory mortars. The binders have apparent d. 2.13-2.18 g/cu cm, porosity 21.4-23.8%, compressive strength 223 71 kg/ sq cm, total shrinkage 0.2-0.8%, and refractoriness 1240 deg

Pawelek, A.

Soltysik, B.

Witkowska, E.

English

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https://ntrs.nasa.gov/search.jsp?R=19830022390 2020-03-21T03:16:28+00:00Z
IOF. POOR QUALITY
:aA TECHNICAL MEMORANDUM
	 NASA TM-77063
PRACTICAL ASPECTS OF THE USE OF PHOSPHATE BINDING MATERIALS
IN REFRACTORY MIXTURES, MORTARS AND PUTTIESS
Elazej Soltysik, Alicja Pawelek, Elzbieta Witkowska
Translation of "Praktyczne Aspecty Stosowania Spiow
Fosforanowych w Masach, Zaprawach i Kitach Ogniotrwalych,"
Polska Akademia Nauk - Oddzial w Krakowie, Prace Komiski
Ceramicznej , (,Serja)Ceramika, Vol. 28, 1978, pp. 101-IO
R q^^ X983
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D. C. 205+6	 JUNE 1983
(NASA-TM-77063) PRACTICAL ASPECTS OF IAE
	 N83-30661
USE OF PHOSPHATE BINDING .MATERIALS IN
REFRACTORY MIXTURES, MORTARS AND PUTTIL
(National Aeronautics and Space
	 Unclas
Administration)
	 I  p HC A02/MF A01 CSL:L I IG G3/27 28408
11
OF POOR QUALITv,	
STANDARD TITLE PACE
ji
l^
if
1. Report me. 2. Government Accession Me. 31 	 Reciplo"I's Catalog No.
NASA TM-17063
4- Title *►NJ Subtitle PRACTICAL ASPECTS OF THE* USE 3• Report Dolo June	 1983OF PHOSPHATE BINDING M,! TERIALS IN RE—
6, Performing Organisation Code
FRACTORY MIXTURES, MORTARS AND PUTTIES
7. Author(@) Blazej	 Soltysik,- Alicja Pawelek ,, 1. Performing Organization Report Me.
Elf biota Witkowska
10. Work Unit He.
9, Performing OrSoMsolson Home and Address 11. C^lroet or Orel I*.
'ijeo- Ranner Associates X
N. Type of Report and Period CovereliRedwood City .,	 CA	 94063
Translation
12. Sponsoring Ag ency Name and Address'
National Aeronautics and Space
Washington, D.C.	 20546 14. Sponsoring Agency CodeAdministration,
15. Supplementary Notes Translation of "Fraktyczne Aspecty Stosowania
Spoiw Fosforanowych 'w Masac•h ,  Zaprawach i Kitach Ogniotrwalych
Polska Akademia: Nauk - Oddzial w Krakowie, Prace Komisici
Ce-amiczrfej, (Seri a) Ceram ika, Vol 28, 1978; pp. 101-107
16.	 Abalicel
Phosphate binders, particularly , acidic phosphates of Al and
Cr, are used for binding Al sii cat.e refractories used for
lining of burnors,-SiC refraotories, and refractory mortars.
The binders have apparent, d.	 2.13-2.18 g/cm3, porosity
21.4-23.8%,	 compressive strength 223 71 kg/6m 2 ., total
shrinkage 0. 2-0. 8%,	 and vefractorines•s '124 00.
17. Key Words (Selected by Autharw) 10. Distribution Statement
UnclassifiQd-Unlimited
It.	 security Cl*ssif. lof this CC. 20.	 Socwrily Clossil. (of this page) 21. No. of Pages 22.
Unclassified Onclassified,
I I	
I
X.,
Wo%^;ivAL FACIt IS
OF POOR QUALITY
PItAOTTOAL ASPECTS OF THE USE OF PHOSPHATE I1 NDTNG MATERIALS
IN 7iEVRAO TORY M I; XTURNSs MORTARS AND PtTTT TXS
WON : of yalk, 11110 ja PawoloRs HImblota Witcawsk,l
Refractory Materials `Tnst;Ituto, llllwim,
Tntroducttczar	 /101*
Phosphate b I nd I nv Mat or l al s , and part l oUlav ly the binder's
0onLa ni; g , old aluminum and rilxt omlum phosphates, have Boon more
and Il1ovo widely ur till In vocont+ Woo t`ov the pmduc` l on of r e-
Pr aotor'y lining Mixtures,  ll or't ar and put t:los.
WILL11J.11 Ilnlust,r pal hosts, pIjoophaTo bI.ratt:ing an,rtt?t y lals have boon
a) :llumino- l lloato mIx tur os fop lining Taut wind rtovolos In
blast; :Pum,toon;
b) Mortars fop joining „-I7.loon carbide o:hoaltonto In ""t'Iaedol
furnace ; providod Vora
 mo lt: lnq z i no-o arvying materials;;
Q puttlos fop
 filling taovatohov, ovacks and .f.AsBuvos In
auxl t l avy ,P o f`p a otor'y m;a t or''tals ur tact in baking oov aml s.
Alluun'i. ►acav`I`I.loato M;Ixturow Based on Phosphate Bindery Used t'oy Lining
For the .. I nt ovlov a.°i t 1-I-Ir of blast Purna00 nov:;los Quyovo ) there
are used Ill p r osont Industrial pr aot;loo, In general, r efraotory con-
crotos latlsod on a1umino-va lci l'ovou a c omonts on vol tivoly Mork
r'up o ly, a1."m1 Baca-s:1 °ll o a;t,c tealxt,uros based on rvator-g lass with or without;
the addition of Al POV
	
Uncles of tla o RAnd work without tr oublo /102
Numbers In tats margin indicate  I*agination In tho foreign text.
1
U^•
or 'POOR govt
lo ll t , ho avol'Stgo, At lllto t l I-,' m olltllll. Tho 01 kobl.colll for 1110 ` t ro ox—
tk'11tli oll of 1'to v1`tlto•to1`y 1111 -Ine"11 :111 >o;lmM, A11, 11tw o 110 1t;MIt's 'ls, t11('1''k'f o1't",
to.1' gv ollt Imp ol't1111t'k' to t'limil't' t'•Ilt' (I olit-IlIv1It.V or tho tu'v o1'%+ 1<lkolllloet'1k,Voll
w;to t t t1 ko^^t^^'^^^'^ kph .
►^ko111ko t^ t';ll'tl >L1;t o , 111kl^itltl 1 tl1 1'to 1,;k'tl1`koll was t al'1' I od kollt, 111 th o	 t
1111obvol^11
	
tool	 kill p oml 11)1.1'I't I ots tart' lltr ' 111'; 1't'^r1'11r!'ottovy alvillibl o-
Ml loot k' 111I'xtt11't'tl but'lkokl oil Io llk o tllo lllltto 11111k1t'L'll for 1111'1111:, >01.11nt r111'1ltw o
11ko t• 1VIllk1 llko ,t;;1k':o.1 ^1111t';l'111i1U1111 I^' k`1'ko totl^- ttt'k'.t,.lkoll ko:t' t1 to "l ant rltl'i1Rt^t'
t=11 \`t o1't' W 11 11 1l 1'k't'1'11t't;k o l.` y A1.11111po; hi to)lowll All 1'111-';ill'k'
/:it1
I"' I P;U1`N `1.	 11 m"'t . 	 I tlyk,vo till lloo t. kill.
Koy (11) 'tko to l ,1tlk'1.t't;	 (b) lit' r1'tlotkol`y `-111111'
I^ 11 tit'tl on 1.111:oko1`11'tko l°y k'll't'l'`Ililk`1l1 , 1;1 ^ 11 1111 t t;111'k> fi k ,, kok' 1;K't' "t•c kl totoll-
1:11111t11 about 4o t r 11 1 41111 1 1 110 --t^ I 1 `1 t":ll t' 1`:'11k^ 1111tt k'1''I 111t: i1nd , bout, ? l0	 vo -
l ao ttol'y tit l ty 11111"t•k'1' 111.1 v, 	 Tho lttttt''It I ko11 OV I*x oKoll l o lito tl o11k1t t'- lrlLlli11111?-
ko lii'c o ill-111111 1> 111d o1' wl 1 10-A 1 1% and "t ho tli vt1 t,°1ko11 to :t' watol' t•t lkl Ilota ox' -,t`od
;.. !	 Tll koldo,4 ' tko toot'M1,l x111 "Wk ok11111'tt' ^Ik`t`-vok` ^o:l' llltot:'111111x1^o111 	 la'k'll1`;l,Il
11nd, "(s old" sol t 1111;; iop ot'll, m ov oo4r ovI 'I. tko , % I e"o wzw added ", 111`t`^ `1111`I.1jLl1'`I ^ 1J
v o11 a't ok1 11111 1:lion 1:';v o mikl to A p,l'<llil Ant 1ko ll bo." tow tl. 111111. t1-molt l ho ,,, 1)1111t tom-
11111i11Illt>-t` 111 , 0111 -111111 >o 'lllklor 1".1`toklllt^ood by T011," 11 11_I,C't?^o.Iloill" 111 I'l of 111tH,
ORK'INAL PA^4:- IS
OF POOR QUALITY
of a density 1.56 MY . was used In both laboratory experiments and
Industrial tests.
The alumino-silicate mixture provided for ramming, with an
addition of 10 -15% green phosphate-alumino-chromium binder, used
w industrial tests for lining blast furnace hot wind nozzles In
the "Bobrek" Steelworks showed, after being baked at a temperature
of 1,000-1100°C (working temperature of hot wind nozzles), the following
properties:
open porosity
apparent density
compressive strength
total contraction (in drying and baking)
regular refractoriness
refractoriness under load
resistance to thermal shocks
( 8 5 00C - water)
21.4 - 23.8%
2.13 - 2.18 No?
223 - 271 kg/cm 2	 L03
+0.2 - +0.8%
156 - 158	 sly
1240°C
more than 10 heat changes
The blast furnace tuyeres with the above-mentioned alumino-
silicate lining based on Green phosphate-alumino-chromium binder
Korkod without trouble for about 2-4 months, thus proving that the
phosphate-alumino-chromium binder may be used in alumino-silicate
mixtures provided for lining blast furnace hot wind nozzles.
Within the scope of laboratory experiments, similar mixtures
based on a white phosphate-aluminium binder were also tested. Never-
theless, despite satisfactory Pcoalts in laboratory experiments, the
alumino-silicate mixture based on white phosphate-aluminium binder
did not prove useful in industrial conditions. The Introduction of
such setting accelerating additives as aluminium oxides, hydroxides
and fluorides, magnesium salts, boric acid and its salts to the mix-
tures based on white phosphate aluminium binder also did not give
satisfactory results.
"I:3
OF, POOR QUAUTY
The reason for this is the fact that the phosphate-aluminium
binder has an insufficient adherence to steel plates and a too small
capacity of binding the alumino-silicate material in the low tempera-
ture range, in contrast with the phosphate-alumino-chromium binder
which creates with the addition of MgO, even at :Low temperatures,
good set mixtures adhering to the steel jacket of the blast furnace
tuyere. This has been confirmed in supplementary laboratory experi-
ments which proved that the adherence of alumino-silicate mixtures
based on phosphate-a.l.umino-chromium binder is about 5-10 kg/cm2 and
their compressive strength about 10-20 kg/cm2
 higher than the respective
properties of mixtures based on white phosphate-aluminium 'oinder.
Mortars for Joining Silicon Carbide Elements in "Thede" Furnaces
Provided Tor Melting Zinc-Carrying Materials
"Thede" furnaces are provided for melting zinc-carrying melting
losses and dusts. These furnaces are membrane-heated in the tempera-
ture range 400-800°C and they work in a slightly oxidizing atmosphere;
the refractory interior lining of silicon carbide is exposed to the
action of metallic Zn, Cd and Pb and oxides of these metals and, more-
	 r
over, to abrasion by the charge. A diagrammatic cross-section of a
"Thede" furnace with the refractory lining is shown in Figure 2.
F
Of essential importance here is the tightness of joints and low /104
porosity of the Joined refractory lining elements made of silicon
carbide, because otherwise zinc may penetrate to the cast iron drum
causing its destruction due to the formation of the "porridge"-like
intermetallic combination FeZn2.
So far, to join
used with the addit
or with the addition
perature.
the refractory lining elements mortars were
ion of silty raw materials or Portland cement,
of water-glass for reducing the setting tem-
4
ONIGNAL	
'%J1
OF POOR QUALITY
Recently ,  industrial tests on the use of phosphate mortars for
Joining silicon carbide elements in "Thede ll
 furnaces for melting
zinc-carrying materials were carried out in the "Silesia" Ceramic
Works in Katowice. The mortar used contained 70-90% silicon carbide
and 10-30% refractory materials.
(a)	 ..	
=
	
t 	 %
Figure 2. "Thede ll
 furnace for melting zinc-carrying materials
Key: (a) Cast iron drum; (b) Refractory lining
The addition of white phosphate-aluminium binder was 25-35% and
the amount of added water never exceeded 10%. White phosphate
aluminium binder produced by IChN "Sulfochem" in Poznan, of a density
1.45 V;/cm 2 , was used in the test.
The mortar used showed high adherence to the silicon carbide
elements and sufficient adherence to the cast iron drum of the rotating
"Thede ll
 furnace, both after drying in open air and after supplementary
drying by means of electric lamps.
The "Thede ll
 furnaces in which mortars based on white phosphate-
aluminium binder were used proved to have a service life of about
9 0 -95 days, whereas the average working time of those furnaces with
5
^	
F :q ^^yr ► 4Y w	
Nk-^ ^OF pOOR Q^ A
"non-phosphate" mortars was only '10-80 days. The obtained results
confirmed, thus, the possibIlity of using mortars based on white
phosphate-aluminium binder for ,loaning elements made of silicon carbide
in the "Thede" furnaces provided for melting zinc-carrying materials.
It should also be mentioned that the upper limit of the lifetime of a
"Thede" furnace also depends to a high degree on the durability of the /105
cast iron drum, partly "limiting" the life of the whole set.
The industrial tests were preceded by broad laboratory experiments
which proved that the mortars based on white phosphate-aluminium binder
distinctly increase their binding properties after roasting in the
temperature range 400-500°C. This results from the dehydration process
occurring in two phases:
a) at the beginning in the temperature range 200-400°C, in
conformity with the reaction:
2A1(H2PO 4 ) 3 =Al 2 (H2 P 2 0 2 ) 3 + 3H20 with a strong endothermic effect,
b) then in the temperature range 400-600°C, in conformity with
the equation:
Al 2 (H2P 2 0 7 ) 3 = 2Al(P) 2 ) 3 + 3x20 with a poor endothermic effect.
The process of white phosphate-aluminium dehydration with the
eduction of an adequate quantity of water provides for compaction
of the grains of the mortar falling agent, thus c.r.eating a joint
that makes a monolithic unit of the ,joined elements. The roasted
r-
mortars also did not show any tendency to repeated dehydration, even
after a longer contact (up to 30 days) with a humid ambient atmosphere.
The laboratory experiments also covered mortars based on green
phosphate-alumino-chromium binder. The results of these experiments
are to be recognized as rather negative, because in the temperature
rang y above 600-800°C the green phosphate-alumino-chromium binder lost
its cohesion somewhat in the presence of Zn+ZnO, thus enabling the
penetration of liquid zinc into the interior of tested samples made
of silicon carbide to a depth 2-3 mm already aster 4 hours of action.
6
ORIGINAL
OF 
POOR rr	 MvY R
In such a situation the green phosphate-alumino-chromium binder has
been excluded from industrial tests on mortars for the "Thede"" fur-
naces for melting zinc-carrying materials.
In order to increase the life of the cermic lining, the interior
of the "Thede"" furnace was additionally coated with a special protective
mixture, containing fine-grained silicon carbide and white phosphate-
.	 j
aluminium binder in an amount up to 50%. This mixture gave, after
drying, a compact coat reducing the penetration speed of 'she "Thede"'
furnace's melted charge into the interior of the silicon carbide re-
f
fractory lining.
Putties Based on Phosphate Binders for Filling Scratches, Cracks
and Fissures in Auxiliary Refractory Materials Provided for Baking
Ceramics
The method of filling scratches, cracks and fissures in refractory
materials depends, e.g., on the method of putting on the putties and
the size of the filled scratches and cracks. The putties can be put
on in various ways, the best method proved to be, however, to "lute". 1106
After the putty has been put on, the products are once more baked in
a temperature range not less than 400-600°C, in order to prevent the
possible dehydration of the phosphate binder. f
The luted putty layer shows high adherence to the base, giving
a uniform potsherd without any effects. No flaking off or loosening
of the putty layer was noticed in the filled places.
t	 At present, the ZMO of Gliwice uses this kind of putty based on
E
white phosphate-aluminium binder for filling cracks and fissures, as
well as scratches on some thin walled products and refractory materials
for baking ceramics, including refractory casings for baking table
ceramics. A diagrammatic cross-section of a silicon carbide casing
for baking table china is shown in Figure 3.f	 r
7
ORIGNAE:
POOR QUAL-iTy
157- 360 mm
129-332mm
c - 28" 75 mm
d- 9-404"
•- 7 -14   mm
Figure 3. Silicon carbide casing for baking table china.
The laboratory experiments carried out proved that for products
working in a changeable atmosphere it is more favorable to use white
phosphate-aluminium binder, but in the case of an oxidizing atmosphere
or in low temperature ranges very good results are obtained when using
green phosphate-alumino-ebromium binder that shows, moreover, very
favorable binding properties also in a lower temperature range. Never-
theless, indpendently of the kind of phosphate binder used, each putty
layer has to be roasted in a temperature range not less than 400-600°C,
in order to eliminate the tendency to dehydration. In the temperature
range 400-600 1 C there also occurs a total dehydration of acid aluminium
phosphates with formation of anhydrous aluminium metaphosphate .., thus
increasing the durability of the joint joining the elements in a
monolithic unit.
8
k•r"
REFERENCES
1. Pawlowski, S., B. Soltysik, "Use of phosphate binder for	 /10
manufacturing refractory and special materials," Report
1621/1130/72.
2. Soltysik, B., A. Pawel.ek, "Refractory mixtures on phosphate
binders for lining hot wind nozzles in blast furnaces,"
Report 1776/2930/74.
3. Soltysik, B., A. Pawelek, "Elaboration of binder based on
phosphates for joining silicon carbinde elements,"
Report 1696/1230/75.
4. Pawlowsik, S., "Aluminium orthophosphate as a new material in
refractory ceramics," Report 744/B-377/64.
5. Budnikow, P.P., "Refractory concretes on phosphate binders,"
Moscow, 1971.
Yr	 4
OF PUGR k h z ve k y
Q9


Practical aspects of the use of phosphate binding materials in refractory mixtures, mortars and putties

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