References cited in this section

65. D.G. Bhat, Chapter 2, in Surface Modification Technologies, T.S. Sudarshan, Ed., Marcel Dekker, 1989, p
141-208
66. T. Takahachi and R. Kamiya, J. Cryst. Growth, Vol 26, 1974, p 203-209
67. H.O. Pierson and A.W. Mullendore, Thin Solid Films, Vol 95, 1982, p 99-104
68. K. Voigt and R. Westphal, Proceedings of the Tenth Plansee Seminar, Vol 2, Risley Translation 4877,
1981, p 611-622
69. D.G. Bhat, Surface Modification Technologies, T.S. Sudarshan and D.G. Bhat, Ed., The Metallurgical
Society, 1988, p 1-21
70. H.O. Pierson, in Chemically Vapor Deposited Coatings, H.O. Pierson, Ed., The American Ceramics
Society, 1981, p 27-45
71. E. Randich, Thin Solid Films, Vol 83, 1981, p 393-398

Thermoreactive Deposition/Diffusion Process for Surface Hardening of Steels

Tohru Arai, Toyota Central Research and Development Laboratories, Inc.; Steven Harper, Arvin TD Center, Arvin Industries

Introduction

THE THERMOREACTIVE DEPOSITION/DIFFUSION PROCESS (TRD) is a method of coating steels with a hard,
wear-resistant layer of carbides, nitrides, or carbonitrides. In the TRD process, the carbon and nitrogen in the steel
substrate diffuse into a deposited layer with a carbide-forming or nitride-forming element such as vanadium, niobium,
tantalum, chromium, molybdenum, or tungsten. The diffused carbon or nitrogen reacts with the carbide- and nitride-
forming elements in the deposited coating so as to form a dense and metallurgically bonded carbide or nitride coating at
the substrate surface.

The TRD process is unlike conventional case-hardening methods, where the specific elements (carbon and nitrogen) in a
treating agent diffuse into the substrate for hardening. Unlike conventional diffusion methods, the TRD method also
results in an intentional buildup of a coating at the substrate surface. These TRD coatings, which have thicknesses of
about 5 to 15 μm (0.2 to 0.6 mil), have applications similar to those of coatings produced by chemical vapor deposition
(CVD) or physical vapor deposition (PVD). In comparison, the thickness of typical CVD coatings (usually less than 25
μm, or 1 mil) has about the same range as TRD coatings.

Process Characteristics

The hard alloy carbide, nitride, and carbonitride coatings in the TRD method can be applied to steels by means of salt
bath processing (Ref 1, 2, 3, 4) or fluidized beds (Ref 5). The carbide coating by salt bath immersion was first developed
in Japan and used industrially almost 20 years ago under the name of the Toyota Diffusion (TD) coating process (Ref 1,
2). The TD method uses molten borax with additions of carbide-forming elements such as vanadium, niobium, titanium,
or chromium, which combine with carbon from the substrate steel to produce alloy carbide layers. Because the growth of
the layers is dependent on carbon diffusion, the process requires a relatively high temperature, from 800 to 1250 °C (1470
to 2280 °F), to maintain adequate coating rates. Carbide coating thicknesses of 4 to 7 μm are produced in 10 min to 8 h,
depending on bath temperature and type of steel. The coated steels may be cooled and reheated for hardening, or the bath
temperature may be selected to correspond to the steel austenitizing temperature, permitting the steel to be quenched
directly after coating.

Salt bath temperatures can also be lowered to the tempering range of steel (Ref 3). In order to lower salt bath deposition
temperatures, techniques to produce alloy carbonitride coatings are used. Such coatings are applied to hardened and
nitrided steels in vanadium-containing chloride baths at temperatures of 550 to 600 °C (1020 to 1110 °F). This section
deals exclusively with coating at a high temperature.