PHOSPHATE-BONDED F. A. Yu. Kh.

REFRACTORY Abzgil'din, Biglov, and R. L. A. B.

COATINGS Amirov, Khoroshavin UDC 666.76.669.056.9

Some r e g i o n s of new t e c h n o l o g y r e q u i r e r e f r a c t o r y c o a t i n g s with w o r k i n g t e m p e r a t u r e s up to 1800~ and a b o v e . H o w e v e r , f r e q u e n t l y in s e l e c t i n g c o a t i n g s the t e m p e r a t u r e of f o r m a t i o n is a c r i t i c a l f a c t o r . F o r e x a m p l e , c o a t i n g s a p p l i e d to l o a d e d , h i g h - t e m p e r a t u r e units and c o m p o n e n t s s h o u l d f o r m at a t e m p e r a t u r e w h i c h d o e s not a f f e c t the m i c r o s t r u c t u r e and b a s i c s t r e n g t h c h a r a c t e r i s t i c s . For most construction heatr e s i s t a n t a l l o y s t h i s t e m p e r a t u r e d o e s not e x c e e d 600-800~ These requirements bonds. T h e r a p i d e x p a n s i o n of the u s e of r e f r a c t o r y c o a t i n g s with p h o s p h a t e bonds is due to t h e i r s u b s t a n t i a l bonding and a d h e s i v e c a p a c i t y , which is m a i n t a i n e d at high temperatures, t h e i r m o d e r a t e s e t t i n g t e m p e r a t u r e (not e x c e e d i n g 600~ the p o s s i b i l i t y of v a r y i n g the p r o p e r t i e s in w i d e l i m i t s by i n c o r p o r a t i n g q u a l i t a t i v e l y and q u a n t i t a t i v e l y d i f f e r e n t a g g r e g a t e s . T h e b a s i c e x p e r i m e n t a l d a t a and t h e o r e t i e a l c o n c l u s i o n s on the p h y s i c o c h e m i e a l p r i n c i p l e s and t e e h n o l o g y of p r o d u c t i o n , and a l s o the t e c h n i c a l p r o p e r t i e s of p h o s p h a t e bonds h a v e b e e n both c o l l e c t e d and T A B L E 1. S o m e P r o p e r t i e s Processing of P h o s p h a t e C o a t i n g s S e t t i n g d u r i n g H e a t a r e m o r e c o m p l e t e l y m e t by r e f r a c t o r y m a t e r i a l s with a d d i t i o n s of p h o s p h a t e

Material* state of the

Composition ofcoating, partsb ~ = ~ ~' materialsurfacevolume ~ o ~

, U [ ~ ~ ~ i/N, o "o "~ o ~o o

~_

I ~ ~'-M '~ ~1 ~

Alloy

V6 underlayer Nichrome underlayer

1Khl8N9T Tungsten

MgAi204:HsPO~ = 1:0,8 MgAl~O4: H3PO4 = 1: 0,8 ZrO~:HaPO4= 1:0,85 ZrQ:PEE = 1:9 ZrQ:Ti:ACPh = 1:0,2:1 ZrO~:Cr:ACPh= 1:0,2:1 ZrO~:Ni:ACPh =1:0,2:1 Cr2Oa:CF:PEE=1:0,2:1 MoSi2: ACPh = 1:0,8 ZrO~:Ni:ACPh =1:0,2:1 ZrO~:Ti:H3PO4=I:0,2:I ZrQ:Cr:ACPh = 1:0,2:I ZrO~:Ti:ACPh =1:0,2:1 ZrO~:Ni:ACPh =1:0,2,1 ZrO2:SisN4: 1Khl8N9T:HaPO~ = 1:0,4:0,2:1,3 ZrO2:Si3Nt:Cr:HzPOt = 1:0,4:0,2:1,3 MoSi~:H3PO4 ~ 1:0,8 MoSi2:H3PO4 ~ 1:0,8 AIiO3:BN:H3PO~= 1:0,4:t,1

500 500 500 300 400 400 350

56 6,9~7,3 82 96 75 16,6--7,5

12501250 1550 1550.

86 7,3--8,5 1350 87 7,6--8,6 1550 92 7,9--8,7 1250

Bronze Br. Kh08

Tungsten underlayer

350 16410 6,8--7,7 1401} 600 36 6,5--8,6 1800 400 7,9--8,7 1250 500 I 92 7,3--8,1 I350 400 135 7,6--8,6 1550 400 131 17,3--8,5 1350 350 110 j7,9--8,7 1250: 600 600 600 600 600 45 6,3--7,8 140ff 37 6,2--8,8 1550, 99 15,1--6,3 1801:}" t42 5,1--6,3 I800 143 5,0--6,3 1650' Translated from

Nichrome

Titanium

V6 V6

Molybenum Graphite

V4 Grinding

S. O r d z h o n i k i d z e U f i m s k A v i a t i o n I n s t i t u t e . O g ~ o . 4, pp. 5 0 - 5 4 , A p r i l , 1973.

E a s t e r n I n s t i t u t e of R e f r a c t o r i e s .

' 9 1974 t Bureau, a division o f Plenum Publishing Corporation, 227 g/est 17th Street, New York, N. Y. 10011. 9~4 Co Consultants No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by an?" means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission of the pablisher. A copy of this article is available from the publisher for $15.00.

253

T A B L E 2. S o m e P r o p e r t i e s Tempe ratu re

of Phosphate

Coatings Setting at Room

Material*

Composition of coatings, parts by volume NiO:Ni:APh = I : 0 , 2 : 1 NiO:Ni:HsPO~ (40%) NiO:Ni:APh = 1:0,2:1 CalrOa:CuO:HsPO~ (75%) = 1:0,4:1,1 1:0,2:1 =1:0,2:1

hear Working rength,

g/era =
16,5 15,4 7,3 25,0 la,3 6,4

tt::Poeca1100 ll00 1100 900 900 600

Alloy 1Kh18N9T
AlloyEI-703 AlloyEP-99

= 1:0,2:1

Titanium VT-9, NiO:Ni:HsPOa (40%) OT-4 Titanium VT-9, F%Oa:Cr: HaPO 4 (75%) OT-4 *Standard of surface finish V 3.

TABLE 3. Some Properties of Phosphate Electric Insulating Coatings B a s e d o n A[203

Coating

)
2 0

summarized in the literature [1,2]. Recently results have appeared from many experimental and theoretical researches dealing with a study of various refractory materials with phosphate setting [3-11]. However the literature does not contain any actual compositions for coatings suitable for many metals and alloys. In particular there is no data for alloys 1KLI8NgT, 1~I-961, I~P-99, EI703, titanium, molybdenum, bronzes, and graphite. The development of refractory coating compositions with phosphate bonds for these materials is dealt with in the present article, and we were faced with the problem for some of them of obtaining coatings which set at room temperature. The main criteria for the suitability of the compositions for use as coatings were taken to be strength (adhesion and cohesion), and thermal-shock resistance.

AIIo)

~ond .~olid: Liquid Iratio

Tfliquid

Et-961

HsPO4 3:1 APh 3:1 PEE 3:1 PEE APh 3:1 3:1

200 200
300 300 200 200 200

111

92 96

VT-9

120 72 102 98

tKhlSNgT aCPhH PO'ItI

Following studies by trial and error we evolved a series of systems satisfying the technical requirements. The starting materials were the following compounds: oxides of zirconium, hafnium, chromium, calcium, magnesium, aluminum, nickel, copper; carbides of hafnium, silicon, boron; nitrides of hafnium, boron, silicon; mullite, magnesia spinel; zirconates of calcium, barium, strontium; disilicide and disulfide of molybdenum; and calcium titanate (3CaO 92 TiO2). The compositions containing the zirconium dioxide also contained powders of some metals (titanium, chromium, iron, nickel, niobium) and mullite fibers. We used reagent grade, chemical-purity, and chemical analytical purity materials. Mullite, spinel, and calcium zirconate and titanatewere synthesized bythe high-temperature firing of stoichiometric mixtures of the appropriate oxides and carbonates. Complete synthesis of the resulting materials was checked by X-ray and petrographic methods.
E

* Surface finish of the alloys EI-961 and VT-9 V8, surface of alloy 1Khl8NgT treated by sand blasting. 1" The basis of the coating (solid) consisted of c~-A89

F i g . 1. T e m p e r a t u r e d e p e n d e n c e of t h e e l e c t r i c a l r e s i s t a n c e of c o a t i n g s . Compositions of the

coatings: I) HfO 2 + PEE; 3) MgO+Al203+ACPh; H3PO 4 (85%).

'C'

2) AI203 + H3PO 4 (85%); 4) MgO+Al203 +

K
o

"-4.
200 400 600 800 IOOO~

254

~'~ Zr0,'Cr /
2o o<.> <~ <.~

zre,-eZ /~
.~,,,>z,~>/,

28 ~

5o 80

o 20 .4o 60 00

Content of metal, vol. ~/o Fig. 2. Relationship between the t e m p e r a t u r e conductivity of coatings and the content of metal and test t e m p e r a t u r e .

All the m a t e r i a l s were ground to obtain fractions < 0.063 mm and then predried at 200~ The powdered zirconia stabilized with calcium oxide (5.16% by weight of CaO) and also metallic titanium and chromium had a grain size of 2-5Ix. The bond consisted of 40, 75, and 85% solutions of H3PO4, an alcohol solution of phosphorus anhyd r i d e - p h o s p h o r e t h y l e s t e r (FEE) and also aluminophosphate (APh) and aluminochromophosphate (ACPh) bonds prepared by the method described in [12]. The ratio of the powders and the liquids used for slaking (solid: liquid ratio) was established in each case starting from the conditions required to obtain a paste of normal consistency. The quantity of solvent per 100 g of dry powder was calculated from the following equation [13]:

v _- ,K( d P, l + ~ P~ +.+~).
where Pl, P2 . . . . . P n is the weight of each filler, g; d l, d21 . . . . d n are the appropriate densities of the powders, g/cm3;and K is a coefficient the value of which depends on the method of applying the coating and the grain size of the powders. F o r powder fractions 2-10t~ the paste of n o r m a l consistency suitable for application of the suspension on the product by brushing was obtained when K = 0.9-1, and with the s e m i d r y p r e s s i n g of the coating on the s u r f a c e K = 0.5-0.6. The surface of the product before applying the coating was cleaned to remove dirt by treating with a c h r o m i u m mixture followed by washing with distilled water and ethyl alcohol. In o r d e r to study the influence of the form of the s u b s t r a t u m on the adhesion we used specimens of bronze Br.Kh08 and steel 1KhlSN9T with coatings applied to them by the plasma method; the coatings were made from tungsten and Niehrome. The specimens with the u n d e r l a y e r were also dried at 200~ The coatings were dried to 250~ at a heating rate of 0.5 d e g / m i n , and at higher t e m p e r a t u r e s at 1 deg/min. Testing of the coatings obtained by this technique on the basis of all the above fillers and bonds showed that compositions given in Tables 1-3 can be taken as the optimum. Table i gives the results of determining the adhesion properties of the coatings (shear strength) , the linear coefficient of t h e r m a l expansion, and the working t e m p e r a t u r e s after heating to which the adhesion of the coating is not less than the original. The coefficient of thermal expansion of the coating was d e t e r mined on a quartz d i l a t o m e t e r after heat p r o c e s s i n g the s p e c i m e n s . The shrinkage and the t h e r m a l expansion factors of the coating depends on the quantity of phosphate bonds, and so Table 1 gives two values for the t h e r m a l - e x p a n s i o n factor: the lower of these c o r r e s p o n d s to the minimum (sem idry pressing), and the higher to the maximum concentration of bond (plastic pressing). By changing the concentration of bond it is possible to v a r y the t h e r m a l - e x p a n s i o n f a c t o r of the coating within the indicated limits. Tables 1 and 2 give working t e m p e r a t u r e s with the m a x i m u m concentration of P205 in the coating. They can be increased by diluting the bonds with water or alcohols. In determining the s h e a r strength we o b s e r v e in the main adhesive failure, that is, the coating breaks away from the s u r f a c e of the product. However, with the use of the sublayer (in p a r t i c u l a r for steels and bronzes) there is cohesive destruction of the coating itself or rupture of the coating together with the u n d e r l a y e r . In c a r r y i n g out tests of the coatings for graphite, destruction o c c u r s at the graphite. F o r the bronzes without the sublayer it was not possible to find a coating p o s s e s s i n g sufficient adhesion at elevated t e m p e r a t u r e s . All the coatings shown in Tables 1 and 2 withstood no less than 6 heat cycles, 600~ The m o s t thermal shock r e s i s t a n t coatings withstood m o r e than 90 cycles, 1200~ - w a t e r . Table 2 gives the compositions, adhesive strength, and working t e m p e r a t u r e s of the coating s e t ling without heating and withstanding not less than 6 heat cycles, 9 0 0 ~ In Fig. 1 and Table 3 the c o r r e s p o n d i n g specific e l e c t r i c r e s i s t a n c e s and bonding strength are given for some coatings designed for securing Nichrome heat s e n s o r s to metals [14]. Of the m a t e r i a l s investigated the maximum e l e c t r i c a l r e s i s t a n c e at elevated t e m p e r a t u r e s is p o s s e s s e d by coatings based on hafnium dioxide and alumina. However the coatings based on hafnium dioxide have unsatis[actory adhesion to the alloys, and do not withstand sudden heat shock as a result of the g r e a t difference in the t h e r m a l - e x pansion factors of the coatings and alloys.

255

Special interest is attached to the coatings based on o x i d e - m e t a l l i c compositions. The addition of powdered metal in all cases i n c r e a s e s the t h e r m a l - s h o c k r e s i s t a n c e of the coatings, markedly improves the cohesion strength and adhesion to all metals. With the addition of c e r t a i n metal powders, for example, nickel and iron, there is a reduction in the heat p r o c e s s t e m p e r a t u r e to room t e m p e r a t u r e , and the c o m p r e s s i v e strength in some coatings (for example, cements of the composition ZrO 2 + Cr + H3PO4) r i s e s to 6000 k g / c m 2, while their t h e r m a l - s h o c k r e s i s t a n c e is higher than that of coatings based on pure oxide. By changing the content of metal it is possible to obtain both heat-insulating and t h e r m a l - c o n d u c t i n g coatings (Fig. 2). We should note that all the compositions with phosphate bonds investigated can be successfully used as c e m e n t - c e r a m i c glues for constructional and nonconstructional joints for different alloys, especially graphite, oxide, and nonoxide c e r a m i c s .

CONCLUSIONS A study of the adhesion and cohesion strength of refractory coatings based on oxides of titanium, zirconium, hafnium, silicon; nitrides of hafnium, boron, silicon; mullite, magnesia spinel, zireonates of calcium, barium, strontium; disulfide and disilicide of molybdenum, and calcium titanate, using phosphate bonds, established the optimum compositions for the coatings for the following alloys: IKhI8N9T, I~I-703, 1~P-99, VT-9, OT-4, ]~I-961, Br.Kh08 bronzes, molybdenum and graphite. Results are given for the working temperatures, shear strengths ,and thermal-shock resistance of the coatings and also the electric conductivity and temperature conductivity of some compositions. The refractory coatings with phosphate bonds that were developed are recommended for use in high-temperature installations in the temperature range I000-1800~ LITERATURE I. 2. 3. 4. 5. 6. 7. 8. 9. 10. II. 12. 13. 14.
CITED

S.L. Golynko-Vol'fson et al., Chemical Principles of the Technology and Use of Phosphate Bonds and Coatings [in Russian], Khimiya, Leningrad (1968). P.P. Budnikov and L, B. Khoroshavin, Refractory Phosphate-Bonded Concretes [in Russian], Metallurgiya, Moscow (1971). P. Bartha, H. Lehmann, and M. Kostermann, Ber. Dtsch. Keram. Ges., 48, No. 3, 111-115 (1971). Karol Berka, Spreehsaal Keram. Glas. Email. Silik., 104, No. 7, 275-276 (1971). I~. M. Verenkova et al., in: Temperature-ResistentProtective Coatings [in Russian], Nauka, Leningrad (]968), pp. 215-222. A.K. Vardenburg and IN. N. Kurochkina, Heat-Resistant and Refractory Coatings [in Russian], Nauka, Leningrad (1969), pp. 434-448. A.S. Mikhailov, Zhurn. Neorgan. Khim,, 13, No. 9, 2356 (1968). F. Yu. Abzgil'din, E. M. Chistova, and S. G. Tresvyatskii, Authors' Certificate No. 234201; Byull. Izobr. i Tov. Znak., No. 3, 155 (1969). F. Yu. Abzgil'din, M. E. Belitskii, and S. G. Tresvyatskii, Authors' Certificate No. 303308; Byull. Izobr. i Toy. Znak., No. 16, 90 (1971). F. Yu. Abzgil'din et al., Authors' Certificate No. 257328; Byull. Izobr. i Toy. Znak., No. 35, 156 (1969). E.P. Mikhashuk et al., Authors' Certificate No. 288628; Byull. Izobr. i Toy. Znak., No. 36, 216 (1970). D. Zh. Gumenika (editor),High-Temperature Inorganic Coatings [in Russian], Metallurgiya, Moscow (1968), p. 220. M.E. Belitskii, F. Yu. Abzgil'din, and S. G. Tresvyatskii, Poroshkov. Metal]., No. 5, 57 (1968). F. Yu. Abzgil'din et al., in: Modern Adhesives and Bonding Plastics and Metals [in Russian], Part I, Znanie, Leningrad (1971), pp. 23-27.

256