Method of applying hard-facing materials
United States Patent 1191 Lally [ll] 3,876,447 1 Apr. 8, 1975 1 i METHOD OF APPLYING HARD-FACING MATERIALS [75] inventor: Frank T. Lolly. Willowick. Ohio [73] Assignee: TRW lne.. Cleveland. Ohio [22] Filed: June 22. 1973 [21] Appl. No.: 372,824  
 Primary E.\&#39;uminerAl Lawrence Smith Assistant Evaluator-K. J. Ramsey Attorney. Agent. or Firm-Hill. Gross. Simpson. Van Santen. Steadman. Chiara &amp; Simpson FORM SLURRY OF PTFE POWDER AND HARD FACING POWDER IN VOLATILE CARRIER DRAIN TO FORM PLlABLE MASS FIBRILLATE PTFE IN MUTUALLY PERPENOICULAR DIRECTIONS 1 1 ABSTRACT Method for applying hard-facing materials to metal substrates through the use of a composite mat consisting of a laminate of two sheets of pliable material. Each of the sheets contains a network of polytetrafluoroethylene fibers which are biaxially oriented. One of the sheets contains particles of a hard-facing material while the other contains particles of a brazing alloy. The laminated sheets are applied to the surface and then the resulting assembly is heated to a brazing temperature whereupon the polytetrafluoroethylene is volatilized and the brazing alloy is melted. producing a dispersion of the hardfacing material particles in a matrix of brazing alloy securely bonded to the substrate. The sheets are prepared by making a slurry of polytetrafluoroethylene particles and hard-facing particles or brazing alloy particles. as the case may be. in  
 combination with a volatile liquid vehicle. After draining off excess vehicle. the resulting limp sheet is subjected to a rolling pressure in two mutually perpendicular directions to thereby fibrillate the resin particles to produce a biaxially oriented network of polytetrafluoroethylene fibers in which the metallic particles are dispersed. A sheet containing the hard-facing particles is then laminated to a similar sheet containing brazing particles. The resulting laminate is then cut to size and applied to the surface of the substrate.  
 8 Claims, 8 Drawing Figures FORM SLURRY OF PTFE POWDER AND BRAZING ALLOY POWDE R IN VOLATILE CARRIER DRAIN TO FORM PLIABLE MASS F IBRILLATE PTFE IN MUTUALLY PERPENDICULAR DIRECTIONS HEAT TO BRAZING TEMPERATURE PAIENIEDAPR 8IEI75 FORM SLURRY OF PTFE POWDER AND HARD FACING POWDER IN VOLATILE CARRIER DRAIN TO FORM PLIABLE MASS FIBRILLATE PTFE IN MUTUALLY PERPENDICULAR DIRECTIONS SIIEEI 1 [If 2 FORM SLURRY OF PTFE POWDER AND BRAZING ALLOY POWDE R IN VOLATILE CARRIER DRAIN TO FORM PLIABLE MASS FIBRILLATE PTF&#39;E IN MUTUALLY PERPENDICULAR DIRECTIONS LAMINATE CUT TO SIZE APPLY TO SURFACE HEAT TO BRAZING TEMPERATURE PATENTEDAPR8|975 $876,447  
 saaasreqgz Fig 3 1 METHOD or APPLYING HARD-FACING MATERIALS BACKGROUND OF THE INVENTION 1. Field of the lnvention a This invention isinthe field of applying hard-facingf within these classes. reference is invited to the Metals Handbook.Eighth&#39;Edition. Volume 1. pages 820 to materialsto substrates and involves the use of a laminated sheet material which can b&#39;e &#39;ap plied in discrete V e e tion is applicable to any of the commonly used brazing which they are to be applied and do not evidence substantial solubility for the hard-facing particles emareas with any configuration desired; L  
 2. Description of the-PriorflArt Hard-facing materials or oxidation protectioncoab ings are frequently applied tovalves or gas turbine engine components by means ofa plasma spray or a flame spray coating process.&#34;Both of these methods result in coatings which contain significant amounts of porosity [The choice of suitable brazingalloys will be governed bythe nature of the underlying substrate&#39;and the invenalloys which are, compatiblewith the substrates on played. The brazing conditions are the same as those and evidence relatively lowbond strengths on&#39;the order of 5.000 pounds per square inch. in addition. these coating processes require facilities which donot lend themselves to production line processing andthey usu-&#39; ally require extensive precautions to protect personnel from harmful rays and excessive noise. The two pro cesses also have the disadvantage-that there is an unavoidably large amount of overspray and thus ineff&#39; cient use of the hard-facing materials: M  
  SUMMARY OFQTHE INVENTION a The method of the present invention involvesapplythe substrate:-  
  ordinarily employed for the particular brazing alloy and bklEhbESCRlPTlON b THE DRAWINGS Other objects. features and &#39;advantages of the inventioitwill be readily apparent from the following de- &#39;scription of certain preferred embodiments thereof.  
  taken in conjunction with the accompanying drawings.  
 although variations and modifications may be effected without&#39;departingfrom the spirit and scope of the novel concepts of the disclosure. and inwhich:  
  FIG. l-is a&#39;yflow chart setting forth the specific steps involved in producingsthelaminate and applying it to thesurfaceztobe hard facedt,  
 ing to the surface of the substrate a mat of biaxially ori ented p0lytetrafluoroethylene- (PTFE)&#34;fibers containing particles of a hard facing material bonded to a mat of biaxially oriented PTFE fibers containing particles of a brazing alloy. and heatingthelaminate to a brazing temperature at which the&#34; brazing-&#34;alloy melts. to  
 thereby volatilize the PTFE and form a coating containing discrete particles of thehard facing materialiin a continuous matrix of brazing alloy bonded to the substrate.  
  The laminate is prepared by forming a slurry of PTFE powder and hard-facing powder in a volatile solvent. After draining to form a pliable mass.the mass is fibrillated in mutually perpendiculardirections by applying a rolling pressure to the mass in such directions. The  
 result is a biaxially oriented sheet ofPTFE in which the hard-facing powder particles are embedded.  
 containing the hard-facing powder. The two sheets are then laminated together by means of slight heat and The temperature is high enough. however, to volatilize off the PTFE. leavinga fully dense&#39;coating consisting&#34; usually of about 80 to 85% by volume iofth&#39;e hard facing particlesand to by volume of the brazing material.  
  The invention is applicable to all types of brazing alloys and hard-facing particles. Any metal. metal carbide. metal nitride or other metal compound which provides a harder surface than the substrate to be coated can be suitably used in the process. Chromium carbide and tungsten carbide are particularly preferred. Metal oxides are not particularly desirable as they are difficult to wet by the brazing metals. Alloys can also be used as hard-facing materials in the new A biaxially oriented sheet containing brazing alloy};  
 particles is produced in the same-manner as the sheet.  
  F lC iS. through ZE-are somewhat diagrammatic &#39;sliowingszof-the methodfioffibrillating the sheets containing PTFEwith the thickness of the sheets being exaggerated for pu&#39;rpfos&#39;es of clarity;  
 FlG.&#34;3w is afra mentary cross-sectionalview of the laminate after ap&#39;plicationto the substrate; and  
  &#34;1FlG.;&#39;4 is a highly: magnified&#39;vi&#39;ew ofthe-microstructure of a coating produced aceording&#39;to&#39;the process of the present invention. I  
 DESCRIPTION OFTHEPREFERRED EMBODlMENTS Referring to FIG; 1. the first step of the process consists&#39;in forming a slurry of IPTFE powder anda hardfacin gpowder in a liquid carrier. The liquid carrier may consist of. materials-such as mineral spirits. Stoddard solyentorother hydrocarbon liquids. The function of the liquid carrier is tolubricate the mass and to soften g upthe PTFE powderforjthelsubsequent fibrillation of thePTEBsThe proportions of the carrier are not at all l.criticallbutno&#39;rrnally about 4 to5volumes of the hy- .dro jcarbonjwill beused for every &#39;volurne ofPTl-E powthen applied to the surface and heated to a brazing temhe e perature which. of course. is below the meltingtemper &#39;j particles&#39;compared-to thePTEE as the amount of hardature of the substrate and of the hard-facing particles.  
  slur ry containsa&#39; lar&#39;ge excess of the hard-facing faeingfrnaterialin&#34;the solids of the slurry may constitute and&#34;.morefwithlvalues of 9&#39;1 to 99357; by weight beingtypical. ThejPTFEjparticles constitute the remain-ingII Ok orle&#39;ssof thesolids of the slurry, and usually about A to3%i by weight.  
  The slurryshouldgbemade up under conditions of high shear agitation as&#39;by use of a blender. The mixing is carried out for periods of time ranging from about i The next step in the process consists in fibrillating the PTFE of the pliable mass in mutually perpendicular directions. This is a technique which has been developed by the du Pont Company and is identified as their HS- l method. A complete disclosure ofthe fibrillating method will be found in Du Pont British Pat. No.  
 l.049.328 which is hereby incorporatedin the specifi;  
 cation by reference.  
 The basic steps of. thei&#39;fibrillating method are. illustrated in FIGS. 2A through 2E of the drawings. FIG. 2A illustrates a pliable mass whichis subjected to rolling pressure by means ofa roller 11 in a lengthwise direction. Typical rolling pressures are about 50 to. I50  
 psi. As illustrated in FIG. 2B. the rollingicauses the.  
 mass 10 to be flattened out substantially into anelongated sheet. Following the longitudinalrolling&#39;. as illustrated in FIG. 2C. the resulting sheetisfolded length wise and then the rolling is resumed in the transverse direction as illustrated in FIG. 2D. Thesheet is&#39;then rolled repeatedly in the transverse direction to produce an elongated sheet which is biaxially oriented and which securely holds the hard-facing particles within its interstices. The thickness of the sheet shown i&#39;nFIGS. 2A to 2E has been exaggeratedfor purposes of illustration. and the normal thickness is less than 1/10 of an inch and usually is about 0.030 inch at the conclusion of the rolling operation. During therolling operation. additional amounts of the liquid carrier can be sprayed onto the mass as needed to maintain workability. The sheet resulting from the rolling operation is a limp. cloth-like mat which is readily handle&#39;able.  
  Returning to FIG. I, it will be seenthat the same type of process is used to form a limp sheet-of biaxially oriented PTFE containing brazing alloy powder. In fact. the proportions of metal to PTFE and all other variables can be the same as in the production of the sheet containing the hard-facing particles.  
 The choice of a particular brazing aIIoywiII. ofv  
 course. depend upon the substrate to which the hardfacing composition is to be employed. Representative brazing alloys are given in the following table:  
  Al ALLOYS I Brazing Alloy Composition Melting Range. F BAlSi-Z 7.5Si.Bal.Al I070 :0 i135 BAlSi-3 lllSiACu. BaLAl 970 to I085 BAlSi-4 l2Si.Bal.Al I070 to I080 BAlSi-5 I IOSLBaLAI 070 to.l095  
 STAINLIVESS STEELS. LOW CARBON STEELS Brazing Alloy Composition Brazing rangclF BAg-l 45Ag.l5(u.  
  lNi.40Cu I575 to I775 BAg-l ll 60AGJUSI1.  
  Cu I325 to I550 BAg-W 92.5Ag.0.2LI.  
  BaLCu loll) to I800 BNi-l l4Cr.4Sl.. .5B.  
  BaLNi I950 to 2200 BNi-3 4.5Si.3.lB.  
 l.5Max.Fe.Bal.  
  Ni I850 to 2l50 BNi-7 l3Cr.lOP.BaI.  
  The two sheets or strips, one containing the hardfacing powder. and the other containing the brazing alloy are then laminated together by means of light rolling&#39;ofn a heated surface. typically at 275 to 325F. At  
 - this stage. each of the sheets has aparticle content of from 40 to 80% by volume, the remainder being the PTFE and void spaces. Thiscomposite sheet can then be trimmed by cutting with a scissors into the shape desired for application to the substrate.  
  FIG. 3 illustrates the composite sheet after its application to a substrate 12. The composite consists of a sheet 13 composed of .fibrillated PTFE containing hard-facing particles and a sheet I4 containing the brazing alloy particles. It seems to make little difference whether the sheet containing the hard-facing part ticles or the brazing alloy particles is placed next to the substrate. The composite sheet may be secured to the substrate by means of a temporary cement.  
  The substrate with the composite sheet attached thereto is then subjected to a brazing temperature appropriate to the brazing alloy being used. In reaching the brazing temperature. the PTFE is volatilized early inthe brazing cycle as is any brazing cement present.  
  The moltenbrazematerial infiltrates the hard-facing particles, Ie&#39;aviriga continuousmatrix of. brazed material 15 in whichl thefdiscrete particlesof hard-facin g material 16 are&#39;jconfined(see-FIG. 4)..The total thickness of the brazedl&#39;coating. should be at least about 0.005 inch and may be ashigh as 0.150 inch. The final coating on;the surface of the substrate isa substantially 100% dense coat typically consisting of 80 &#39;to 85% hardface particles and&#39; l5to 20% brazing material.  
  The use of the compositesheets permits the hard par ticle sheets to be processed to a higher initial&#39;density or hard particle content as comparedwith combining hard particles and brazing powders into the same sheet, in which casepthe sheetis limitedtoa lower density range dependingon the volume of braze material used.  
  The brazing itself may be performed b y conventional torch heating. furnace heating. resistance heating or induction heating. Furnace heating is generally preferred in a vacuum ora reducing orneutral atmosphere to prevent oxidation of the substrate. Brazing by resistance heating has the advantage of rapid heating. minimum cycle timewhich minimizes exposure of the component to hig&#39;htemperature and reduces any tendency of the molten braze material to dissolve or alterthe chemical or physical makeup of the hard-facing particles. I  
 rolling pressure. folding. cross-rolling and refolding.  
 spraying mineral spirits as needed to maintain workability. The rolling and cross-folding formed a network ofTeflon filaments which served to hold the particulate material in place and provided a handleable clothlike mat. This mat had a density of 65% of theoretical and a thickness of 0.030 inch. A nickel brazing alloy sheet was made up to the same sheet thickness and containing substantially the same amount of metal particles as the chromium carbide mats. The two mats were laminated together under slight rolling pressure at slightly elevated temperatures. They were applied to a nickel superalloy base and then heated to a brazing temperature. During the braze cycle. the brazing alloy in the molten state infiltrated the hard particle mat. filling the interstices and forming a coating on the substrate consisting of hard particles in a matrix of the brazing alloy. The Teflon volatilized early in the brazing cycle.  
  Wear tests were conducted to compare the hard-face coatings applied by this process with coatings applied by conventional processes. It was found that the coating produced according to the present invention exhibited a loss of 0.00l 2 inch after a test period of hours.  
 which is comparable to coatingsapplied by other processes.  
  Oxidation-diffusion tests were conducted up to a maximum of 500 hours exposure at 1,700F in air. Visual examinations revealed little damage except for a superficial oxide coating on the surface. Metallographic examination showed no evidence of oxygen penetration. The specimen was recrystallized as a result of the temperature exposure. but showed no other damage.  
  It should be evident that various modifications can be made to the described embodiments without departing from the scope of the present invention.  
 I claim as my invention;  
  1. The method of applying a hard facing to a sub strate which comprises applyingto the surface of said substrate a laminate comprising a mat of biaxially oriented polytetrafluoroethylene fibers containing particles of a hard-facing material bonded to a mat of biaxially oriented polytetrafluoroethylene fibers containing particles of a brazing alloy. and heating the laminate to a brazing temperature at which&#39;said brazing alloy melts. to thereby volatilize said polytetrafluoroethylene and form a coating containing said particles of hard-facin g material in a matrix of brazing alloy bonded to said substrate.  
  2. The method of claim 1 in which the hard-facing material constitutes from 40 to by volume of the mat in which it is included.  
  3. The method of claim I in which the brazing alloy constitutes from 40 to 80% by volume of the mat in which it is included.  
  4. The method of claim 1 in which said hard-facing material is chromium carbide.  
  5. The method of claim 1 in which said coating has a thickness in the range from about 0.005 to 0.150 inch.  
  6. The method of applying a hard facing to a substrate which comprises forming a pliable sheet of hardfacing material particles andpowdered polytetrafluoroethylene. fibrillating the resulting sheet to form a biaxially oriented sheet. laminating the resulting sheet to a sheet of biaxially oriented polytetrafluoroethylene containingparticles of a brazing alloy. applying the resulting laminate to said substrate, and heating the laminate to a brazingtemperature at which said brazing alloy melts to thereby volatilize said polytetrafluoroethylene and form a coating containing said particles of hard-facing material in a matrix of brazing alloy bonded to said substrate.  
  7. The method of claim 6 in which said hard-facing material particles constitute from 40 to 80% by volume of the sheet in which they are included.  
 8. The method of claim 7 in which said hard-facing material is chromium carbide.  
 * i i i i Disclaimer 3,876,-H7.F7*an70 T. Lally, ViHOWiOk, Ohio. METHOD OF APPLYING HARD-FACING MATERIALS. Patent dated Apr. 8, 1975. Disclaimer filed Nov. 22, 1976, by the assignee, TRW Inc.  
 Hereby enters this disclaimer to claims 1l0 of said patent.  
 [Ofiicial Gazette Febmomy 1, 1,977.]