CA2128756C

CA2128756C - Preparation of friction elements and compositions therefor

Info

Publication number: CA2128756C
Application number: CA002128756A
Authority: CA
Inventors: Ralph T. Brotz; Paschal A. Sciarra, Jr.; Philip A. Waitkus
Original assignee: Plastics Engineering Co
Current assignee: Plastics Engineering Co
Priority date: 1994-07-25
Filing date: 1994-07-25
Publication date: 2005-11-01
Anticipated expiration: 2014-07-25
Also published as: CA2128756A1

Abstract

A method for preparing a friction element from rod-like particles of friction ingredients includes preheating the particles, to a temperature between 150°F
and 375°F, introducing a predetermined amount of the preheated rod-like particles into a friction element mold, and compressing the preheated rod-like particles under heat and pressure to form the friction element.
Compositions for forming the rod-like particles are disclosed.

Description

~izs~~~
PREPARATION OF FRICTION ELEMENTS
AND COMPOSITIONS THEREFOR
The present invention relates to new technology and insights which when practiced make possible more efficient and reliable manufacture of molded friction elements for automotive disc brakes, truck brakes, and other friction applications. More specifically, this invention relates to methods for the conversion of the loose, bulky and dusty mixtures as currently used for the manufacture of these friction elements into a more desirable state, namely: densified, cylindrical, rod-like particles possessing physical integrity together with sufficient surface area to enable practical preheating with pressurized gas at elevated temperature immediately prior to mold charging. This results in the production of molded friction elements of better quality and with greater efficiency than previously possible.
Currently, molded friction elements as installed in vehicle brake systems are molded from a blended mixture of friction ingredients that are loose, bulky and dusty blends of resinous binders, reinforcing fibers, friction and wear controlling agents and inexpensive fillers. The mix is loose, bulky and dusty because the ingredients are in the form of fine powders, small and larger granules and fibers.
Powdered phenolic thermosetting resins are the binder of choice for a variety of braking applications.
These heat resistant resins serve to bond the other QB1~5t918.

ingredients into a solid, infusible mass when molded to final shape under the effects of heat and pressure. The reinforcing fibers are used to impart physical strength, heat stability and, to a limited extent, friction properties to the finished element. The friction and wear controlling agents are typically granules and powders of carbonaceous materials which impart and maintain the friction level and wear resistance. The inexpensive fillers are generally powdered minerals used to fill space and enhance some properties.
The formulas of the compositions used to make friction elements for specific applications are usually developed experimentally, confirmed by testing and, to a considerable extent, are held confidential. However, generally accepted volume ranges for the various friction ingredients in the compositions are as follows:
~ Volume Friction Ingredient general preferred Binders 10 - 35 20 - 30 Reinforcing Fibers 0 - 50 5 - 25 Friction & Wear Controlling Agents 20 - 80 35 - 45 Fillers 20 - 70 20 - 30 As a general rule, the binder content of a friction element is kept to a minimum. No more binder resin is used than is necessary to sufficiently bond the other ingredients into a solid, infusible mass when molded under heat and pressure. The minimum binder volume required will be determined by the types of friction ingredients used and, to a large extent, by the processes used to manufacture the final friction element.
Binder content is minimized because the organic resins used may be subjected to temperatures above their decomposition points. Partial decomposition of the binder at high service temperatures results in the QB1151918.

~~&~
r formation of gases at the friction interface which lowers the element's braking effectiveness. This loss in effectiveness at elevated temperatures is referred to as brake "fade". The greater the element's binder content, the greater the effects of brake fade. Also, binders traditionally comprise a large percentage of the friction element's cost which provides an additional incentive to reduce its content.
The general process for the production of friction elements is described as follows: the desired amounts of the powdered binder resin, fibers, fillers and other ingredients are dry mixed. The bulk density of the resulting dry mix, which is a loose, bulky, dusty mass of powder, is less than half that of the molded element's final density. The mix must be carefully handled to avoid settling and separation of its powdered, granular, and fibrous ingredients.
It is current industry practice to first produce from the loose, bulky, dusty dry mix, prior to molding 2o and at room temperature, a fragile preform in the near net shape of the final friction element. The preforms are made to the near net shape of the final element because, as a minimum amount of binder is used in friction elements to avoid brake fade, the dry mix has a very low propensity to flow and uniformly fill the mold cavity when heat and pressure is applied. The low resin content also results in weak and easily broken preforms which must be specially and carefully handled when transferred to a heated mold cavity for forming into final shape. The hot, pressurized molding step causes the resinous binder to melt, flow and coat the material's fillers. The thermosetting resin then crosslinks and cures to an infusible state. After ejection from the hot mold, the element may be cured further in an oven. When cool, the friction element is machined to final size, catalogued and packaged for market.
QB1\51918.

Preforming the dry mix prior to hot press molding helps eliminate some, but not all, of the unwanted air that can otherwise be trapped within the friction element. As the thermosetting resin crosslinks and cures during the molding step, gaseous byproducts such as water vapor and ammonia are produced. These vapors, along with the trapped air in the preform, will, if retained within the molding, result in unacceptable defects in the form of blisters, voids and delaminations in the final friction element.
In an effort to avoid such defects, it is current industry practice to frequently open the hot mold cavity during molding to allow the entrapped vapors to escape.
The mold cavity is then closed and pressure reapplied so the fissures and delaminations created by the escaping vapors are sealed. This repeated opening and closing of the mold cavity is termed "breathing" or "bumping" the press. Press "bumping" cycles are continued until the binder has hardened so that the described defects will not result when the element is ejected from the mold.
Press bumping must be carefully and correctly timed so the resin has enough flow and reactivity to completely seal the voids and delaminations created by the escaping vapors. These delaminations and unsealed fissures will diminish the physical integrity of the element. Also, partially sealed fissures may delaminate when the element experiences rapid frictional heating during service.
This problem has led to recalls of friction elements.
Thus, press breathing, while employed to reduce defects, is time consuming, lowers productivity, and also causes product quality uncertainty.
The negative factors involved with the current methods of manufacturing friction elements can be circumvented by transforming the loose, bulky, dusty mix into a dense, regular geometry that lends itself to preheating prior to mold charging. As preheating starts QB1\51918.

, the binder's curing reaction before the mixture is placed in the mold much less time is required to cure the mass of material to an infusible state. Thus, preheating the mixture is highly desirable because preheating enables more rapid molding cycles. In addition, the number of required press "bumps" may be reduced or even eliminated by preheating the charge of friction ingredients.
While high frequency radio waves, or oscillating magnetic fields, may be used to preheat specific friction 1o material compositions, hot pressurized gas preheat systems appear to be the most economical and universally available method for preheating friction ingredients of all types. The inability to uniformly preheat conventional preforms of dry mixed friction ingredients with hot gas systems results from the mix's low density and subsequent low thermoconductivity. As heat transfer from the surface to the center is poor, simple convection or forced air ovens quickly heat and cure.the binder on a preform's surface while its interior remains cool. Thus, no advantage is realized by hot gas preheating materials produced by the currently practiced dry mix preform method.
Preheating with hot, pressurized gas, requires that the friction material mix be densified in some way to improve its thermoconductivity. However, the densified particles must not be manufactured in a way that reduces the binder's plasticity to a point where the material will not flow and fuse during hot press molding. Also, as the goal is to manufacture friction elements as efficiently as possible, extra manufacturing steps such as filtering, drying, pressing, grinding or classification, which add cost and complexity to the process, should be avoided. In addition, the size and shape of the densified mix must be such that open channels are formed within a material charge to allow the QB1151918.

, , hot gas to freely flow throughout all parts of the charge to assure uniform preheat.
In using hot gas preheat systems, it must be noted that while very hot air would quickly heat the friction material charge prior to molding, the preheat air must not precure the binder on the surface of a densified particle before adequately heating the interior.
Therefore, while the initial thermal gradient from the particle's surface to its center must be relatively low, fast efficient preheat may be obtained by minimizing that distance. However, the particles must not be so small that they are carried away by the gas stream creating dust, or pack in a way to minimize the size of the open channels or cause large channels to form through which most of the preheat air preferentially flows.
A number of methods have been proposed for densifying a mix of friction ingredients. These methods include adding liquid solvents or cements., subjecting the mix to agglomeration techniques, or by extruding or pressing the mix followed by pulverization into a granular material. However, when put into practice these densification methods have been found to be ineffective, mainly because they add costly and complicated drying, recovery, pressing, grinding or screening steps to the manufacturing process. In addition, the densified particles obtained by these methods vary in size from inches in diameter down to small grains. The large particle size distribution results in dust generation and hinders uniform preheating with hot gas because the smaller particles quickly heat while the larger particles remain much cooler.
Thus, the problem lies in how to prepare the friction material mixtures in a way to make preheating with pressurized gas viable. We find that uncured friction material compositions formed into dense, cylindrical rod-like particles satisfies the requirements QB1\5191$.

_7_ needed for efficient preheating with pressurized gas.
The unique shape of the rod-like particles allows the diameter of the particle to be minimized while the length allows for the formation of a homogeneous matrix of air channels within a charge of particles. These rod-like particles are made to regular and uniform diameters on the order of 3/32" to 1/4". If the densified particles are not of the same approximate size, smaller particles will quickly heat and precure while larger particles 1o remain unaffected resulting in a nonuniform preheat which is undesirable. The length of the rod-like particle may vary as length is more critical to particle integrity than to preheat uniformity. We have found lengths of 1/8" to 3/4" to be ideal for this purpose.
It is an object of the present invention to provide a method of preheating particles of a friction material composition and molding those particles with compression and heating into friction elements.
It is an object of the invention to provide particles of friction materials which can be readily preheated and compression molded to form superior friction elements.
It is a further object to disclose novel mixtures of friction materials that can be used to form the desired particles.
We have discovered that dense, regular, cylindrical, rod-like particles of friction ingredients having diameters of from about 3/32" (about 0.20 cm) to about 1/4" (about 0.60 cm); lengths from about 1/8" (about 0.30 cm) to about 1" (about 2.5 cm); and, densities greater than about 70~ of the density of the final friction element can easily be preheated and compressed with heat to form superior friction elements.
The geometry of the rod-like particles allows fast preheating by minimizing the distance from the surface of the particles to its interior while being sturdy enough QB1\51918.

to secure all of the ingredients in place. Also, being of a regular rod-like shape, the particles naturally create and maintain large open channels or passageways so all of the particles have free access to the heated air for fast, efficient and uniform preheating with pressurized gas. When preheated, the particles maintain their free-flowing nature to allow for quick and easy charging of the hot press mold cavity eliminating any need to preform. The uniformity of the preheating of these particles allows for the reduction or elimination of press breathing and for faster molding cycles thereby improving productivity as previously described. In addition, by retaining the plasticity of the particles during densification, the flow of the friction material in the pressurized mold is dramatically improved.
We also have discovered that unexpectedly the combination of regular, rod-like particles and uniform preheating allows lower binder amounts to be used to produce uniform friction elements with unique and desirable friction properties accruing from the lower binder content.
It has heretofore been impractical to extrude friction ingredient mixtures or compositions under pressure into the form of our desired particles because the friction properties of the materials cause the temperature of the extrusion die and associated equipment to quickly reach the cure temperature of the resin binder. As the curing of the resin occurs, a slow buildup of cured friction material on the screws, barrels or extrusion die develops. This has a dramatic and undesirable effect on the maintenance of desired Theological properties and the continued production of useable material. When such buildup occurs the process must be aborted to prevent damage to the equipment or to avoid production of costly unusable material.
QB1G51918.

.
, _9_ We have now discovered that friction ingredient mixtures or compositions in which a small amount of the solid, heat resistant resin binder is replaced with a temperature controlling additive, preferably a thermosetting liquid resin, permits particles of the desired geometry to be made.
The liquid resin apparently lowers the temperature necessary to achieve extrusion rheology of the mix thereby reducing the frictional heat created during extrusion. Thus, the rod-like particles can be produced without the build-up of cured friction material on the production equipment which frequently accompanies such extrusion processes when the compositions do not contain a temperature controlling additive. In addition, using the preferred additive, which is a coreactive, heat resistant liquid phenolic resin, does not introduce any new ingredients into the friction composition which could alter the frictional properties of the finished element during use. Preferably only enough liquid resin is used to maintain the processing temperature below the curing temperature of the solid resin binder. Excess amounts of the liquid resin can diminish the particle's integrity resulting in poor material yields. In addition, any residual liquid may require the addition of costly drying procedures. Furthermore, we have found that the same amount of liquid resin which provides the desired temperature control also enables the formation of particles of the desired density for preheating.
Preferably, the cylindrical rod-like particles contain no more than 15~ by weight of material smaller than 60 mesh and they have diameters of 1/8" to 5/32"
with lengths from 1/8" to 1". The cylindrical rod-like particle's size is determined by the diameter of the orifice used to extrude the mix while its length is controlled by knocking the nascent rod-like particle from the die's surface at a specified distance or after a QB1151918.

certain time. These preferred particles allow for fast preheating by lowering the interior to surface distance while being sturdy enough to secure all of the ingredients in place. Large channels are formed between the cylindrical rod-like particles to allow for uniform preheating with hot air systems with little or no dust contamination to the surroundings. When preheated to a temperature between about 150°F to about 375°F, the cylindrical rod-like particles maintain their free flowing nature to allow for quick and easy charging of the hot press mold cavity. The plasticity of the binders is retained during densification and, as a result of preheating and improved utilization of the binder, the flow of the material under pressure is dramatically improved. xhus lower overall binder amounts may be used .to produce quality friction materials.
The preheated cylindrical rod-like particles can be formed into friction elements by introducing a predetermined amount of such particles into a mold for a friction element and compression molding them under heat and pressure at temperatures of about 250°F to about 500°F or more and under pressures of about at least 700 psi and up to or more than 6040 psi until the resin is infusible.
The uncured rod-like particles of the invention also provide for manufacturing friction elements from mixtures of different types of rod-like particles. These unique moldings exhibit synergistic properties which result from combining different friction materials where one or more of the materials are shaped into the uncured, rod-like particles of xhe invention prior to molding the friction element.
Therefore, in accordance with the present invention, there is provided a method of preparing a friction element comprising:

-lpa-a) forming cylindrical rod-like particles of a material comprising a mixture of friction ingredients, a solid thermosetting resin and an effective amount of a liquid agent which maintains the temperature during rod-s like particle formation below the curing temperature of the solrd resin, said rod-like particles having a diameter of about 3/32" to about 1/4";
b) preheating said rod-like particles;
c) introdurir~g a predetermined amount of said rod-like particles into a friction element mold: and d) forming a friction element by compressing the rod-like particles under heat and pressure until the res~.n has become infusible.
Also in accordance with the present inventionr there is provided substantially dust--free, rod-like particles having a diameter of about 3/32" to about 1/4" and a length of about 1/8" to about 1", said rod-like particles be~.ng of a composition comprising about 5~ to about 30~
by weight of a thermosetting binder resin; and about 1$
to about 50~ by weight of a temperature controlling agent capable of lowering the temperature of the materials during particle formation.
Further in accordance with the present invention, there is pro~rided a composition for forming rod-like particles of friction ingredients, said composition comprising about 5a to about 30$ by weight of a thermosetting res~.n and about 1~ to alao~tt 50$ by weight of a temperature controlling agent which keeps the temperature of the composition below the wring 3a temperature of the resin when the composition is being formed in a pellet mill into rod-like particles.
Still furtrier in accordance with the present invention, there is provided a method of preparing a friction element comprising:
a) forming cylindrical, rod-l~.ke particles of an uncured mix of friction ingredients, a solid -lOb-thermosetting resin and an effective amount of liquid phenalic resin which maintains the temperature of the particle formation process below the curing temperature of the solid resin, said rod-like particles having a diameter of about 3/32" to about 1/4";
b) preheating said rod-like particles; and c) molding the preheated rod-like particles into a friction element.
Still further in accordance with the present invention, there is provided friction elements manufactured from different types of friction ingredients where mixtures of rud-like particles of at least two different friction material formulae are preheated and molded together, each friction material formula i5 comprising a mixturs of friction ingredients, a solid thermosetting resin and an effective amount of a liquid agent which maintains the temperature during rod-like particle formation pelow the curing temperature of the sold resin, said rod-like particles having a diameter of about 3/32" to about 1/4"_ It will be further apparent to those skilled in the art from the description of the preferred embodiment and the examples that the above stated objects are obtained by the present invention and that the practice of the _, ~ ' present invention has significant advantages over current commercial industry practices.
The preferred friction ingredient compositions of the present invention have the following general formula:
~ Weight Thermosetting Resin Binder 5 to 30%
Temperature Controlling Agent 1 to 50~
Reinforcing Fillers 5 to 500 Organic Fillers 0 to 60%
Inorganic Fillers 5 to 800 Many heat resistant thermosetting resins may be used as the binder in the practice of this invention. These resins include unmodified phenol-aldehyde resins,- alkyl modified or inorganic modified phenol-aldehyde resins, epoxy resins, polyimide resins and many others as described throughout the patent literature.
For most applications, unmodified phenolic resins of the novolac type are preferred. The novolac resin is produced by controlling the reaction of phenol and formaldehyde in the presence of an acid catalyst.
However, the amount of formaldehyde employed is maintained at a level which is insufficient to completely form a cured crosslinked structure. These resins are thermoplastic and at room temperature are solid and brittle. To complete the curing or crosslinking reaction, a hardening agent, hexamethylenetetramine (hexa) is added. Hexa is a dry crystalline reaction product of ammonia and formaldehyde. When the mixture is heated in the mold, the hexa decomposes and forms crosslinking bridges of carbon and some nitrogen between the novolac molecules to cure the product into an infusible mass.
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A variety of agents can be used to control the temperature of the mix as it is being formed into the rod-like particles. Representative agents are furfural, diphenyl oxide, furfuryl alcohol, polymers of hydroxymethylfuran, and water oil emulsions. However, the preferred agent is a liquid phenolic resin resole which is prepared by reacting phenol with formaldehyde in the present of an alkali or alkaline earth metal hydroxide or equivalent. One such resin is commercially available from Plastics Engineering Corporation under the trade name PLENCO 12194.
The reinforcing fillers are generally fibers such as asbestos, glass, ceramic, mineral, steel, brass, copper, or heat resistant organics such as aromatic polyamides or acrylic. The organic fillers may include particles from cashew nutshell oil resins, polymerized or partially polymerized, or elastomers in the form of virgin rubbers together with their vulcanizing and accelerating agents or polymerized rubber particles from scrap. The inorganic fillers include carbonaceous materials such as graphites and cokes, metallic powders from iron, brass, copper or zinc, or mineral fillers such as barium sulfate, kyanite, aluminum oxides, marble white, rottenstone, vermiculite, talcs and clays to name a few.
An especially preferred friction resistant compositions of an "organic" type friction material and a "semimetallic" type friction material have the following formulas:
QB1~51918.

, ' -13-weight "o rganic" emimetallic"
"s Powdered Phenolic Novolac Resin to 15 5 to 10 Liquid Phenolic Resole Resin 1 5 2 to 10 to 5 Heat Resistant Fibers 0 to 25 20 40 to Nitrile Rubber 3 to 10 1 to 5 Ground Rubber Particles 0 to 15 0 to 5 Cashew Resin Particles 0 to 10 1 to 5 Graphites and Cokes 0 to 15 5 to 20 Metal Powders 0 to 40 20 40 to Mineral Fillers 10 to 50 0 to 25 Each of the ingredients mentioned above are readily available.

Examples The invention is further illustrated by the following examples, wherein all parts are by weight, unless otherwise specified. Example 1 illustrates the preparation of a preferred friction resistant composition; Example 2 illustrates the preferred particle forming method; Example 14 illustrates the method of molding elements of the preferred composition and Example 15, 16, & 17 illustrate the method of improving the properties of the molded friction elements.
Example 1 Preparation of Friction Ingredient Composition The following raw materials were blended in a mixer to form a dry mix of the preferred friction ingredient composition.
QB115191R.

' -14-Weiq-ht Powdered Phenolic Novolac Binder Resin 14 Liquid Phenolic Resole Resin 1 Ceramic Fiber 22 Mineral Fiber 8 Cashew Nutshell Resin 6 Nitrile Rubber with cure system 6 Ground Rubber Scrap (-20 mesh) 6 Brass Chips (-20 mesh) 3.5 Zinc Stearate (mold release) 0.5 Barium Sulfate 30 Example 2 Preparation of Rod-Like Particles The dry mix of ingredients obtained in Example 1 was fed into the compression zone of a roller-die compression extruder, such as a Sprout Waldron Pellet Mill. Pressure was applied and quality-rod like particles with a density near 80~ their final molded density were obtained. The particles had regular diameters of 1/8" with lengths on the order of 1/8" to 1/2".
Example 3 The Preparation of Rod-Like Particles of Semimetallic Friction Ingredients Without Temperature Control Agent Into a Littleford Mixer was placed the following ingredients:
Phenolic Novolac Binder Resin 62 lbs Nitrile Rubber 17 lbs Steel Fiber 260 lbs Barium Sulfate 97 lbs Aluminum Oxide 7 lbs Iron Powder 260 lbs Graphite 140 lbs This mixture was blended until it was thoroughly mixed, then fed to the extruder of Example 2. After approximately ten minutes, the temperature of the QB1\51918.

~~.~8~~ ~
' -15=
particles exiting the unit exceeded 300°F and the mill ceased functioning. The experiment was stopped to avoid damaging the unit. Attempts to mold the resulting particles resulted in moldings in which the particles would not flow together. The resulting molding crumbled in hand and exhibited no strength.
Example 4 The Properties of Rod-Like Particles of Semimetallic Friction Ingredients with Temperature Control Agent The blending procedure of Example 3 was repeated except that during the blending 3.3~ by weight of a liquid phenolic resin resole (PLENCO 12194) was slowly added to the mixture. This resole is composed of approximately 75~ by weight of resin in a water solution and an equal weight of the powdered novolac resin binder was omitted from the mix. When blending was completed, the mixture was passed through the extruder of Example 3, but this time the material was extruded into shape easily with no trace of curing. The temperature of the exiting particles never exceeded 230°F and when molded filled the test mold completely. When molded as explained in Example 8 and 9, the rod-like particles showed excellent hole filling ability and excellent adhesion.
Example 5 Preseryation of Compound Reactivity Two friction materials, one generally referred to as a semimetallic and the other generally referred to as a non-asbestos organic material were prepared from the following formulas:
QB1\51918.

Semimetallic Friction Material Composition Ingredient % Weight Resin g.5 Liquid Phenolic Resin Resole 3.0 Rubber 1.5 Cashew Particles 1.2 Graphite 13.5 Petroleum Coke 5.3 Barytes 11.5 Steel Fiber 27.5 Iron Powder 28.0 Non-Asbestos Oraanic (NAO) Friction Material Inaredient ~ Weiaht Resin g.0 Liquid Phenolic Resin Resole . 1.0 Rubber 5.0 Mineral Fibers 14.5 Graphite 5.5 Petroleum Coke 4.0 Barytes 28.0 Copper Powder 34.0 A charge of a metallic stearate equal to 0.50 of the total batch weight was added to the above formulas. In applications as a mold release agent, metallic stearates, such as calcium stearate and zinc stearate, have proven satisfactory. One such metallic stearate is commercially available from Plastics Engineering Company under the trade name PLENCO 10915. Metallic stearates have not been shown to affect the wear and friction performance of friction materials when used at this low level.
The formulas were thoroughly mixed in a Littleford blender and a sample of each dry mix was set aside. The QB1\51918.

remaining material was processed into rod-like particles according to the invention previously described.
The degree of reactivity of the Littleford dry mix and the processed rod-like particles is checked by extracting compound samples with tetrahydrofuran (THF) in an apparatus commonly referred to as a Soxhlet extractor.
As uncured resins are extracted from the compound sample the greater the extractable amount, the more reactive the sample. The extractable percentage of the sample is defined by the following equation:
Percent Extractable = 100 x (Wt. Before - Wt. After)/Wt.
Bef ore Wt. Before = weight of sample before extraction Wt. After = weight of sample after extraction The dry mix and processed rod-like particles of the non-asbestos organic and semimetallic materials were tested for percent extractable by the method described.
The results are shown in the following figures:
Rod-Like Non-asbestos Or anic Dry Mix Particles THF Extractable 10.2 10.2 Rod-Like Semimetallic Dry Mix Particles THF Extractable 10.0 10.4 Materials made without adequate temperature control agent have shown dramatic reductions in percent extractables and thus a lowering of reactivity.
Non-asbestos organic and semimetallic formulas identical to the ones described above were processed with water in place of the resole. As the following extraction results show, omitting the resole resulted in particles of lower reactivity. In the case of the semimetallic formula, the reactivity is considerably reduced.
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_ .

THF Extractable Rod-Like NAO Dry Mix Particles With Resole 23.4 23.4 Without Resole 23.2 22.5 Rod-Like Semimetallic Dry Mix Particles With Resole 7.0 6.1 Without Resole 6.9 3.6 From these results, it may be concluded that the particle forming process does not significantly effect the reactivity of the friction compounds when the resole is used.
Example 6 Improved Preform Shape Retention Preforms in the shape of disc brake pads suitable for a Ford F-250 pickup truck, (FMSI #D-120), 0.700" tall with a surface area of 12.8 in2 were formed from both the Littleford mix sample and the rod-like particles of the non-asbestos organic and semimetallic materials described in Example 5.
The preforms were formed under 3,000 psi surface pressure and pressed for 10 seconds. The thickness of the preforms was measured immediately after removal from the mold, after being left to stand for three hours, and again after three days.
The average percent thickness increase of the preforms was calculated. The results are shown in the following tables.
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D-120 Preform % Thickness Increase NAO Formula Dry Mix Rod-Like Particles Averaae Std. Dev. Averaae Std. Dev.
After 3 hours 6.4 2.1 1.4 .5 After 3 days 9.0 3.0 2.3 .2 Semimetallic Dry Mix Rod-Like Particles Formula Average Std. Dev. Average Std. Dev.
After 3 hours 3.3 1.2 2.1 .3 After 3 days 4.5 2.0 3.4 .4 Std. Dev. - Standard Deviation (N-1) Thus, friction ingredients formed into rod-like particles by the above invention demonstrate excellent preform shape retention.
Example 7 Improved Break Strength of Preforms Formed from Rod-Like Particles Preforms for a Ford Escort passenger car disc brake pad (FMSI #D-257) were made from the dry mix sample and from rod-like particles of the semimetallic and non-asbestos organic friction materials described in Example 5.
The 1" thick preforms were made by pressing the materials under 2,500 psi for five seconds in a steel preform mold. The three point breaking strength of the preforms was then measured using a crosshead speed of 0.1 in/min and a span of 2i". The results from the tests are shown in the following figure:
QB1\51918.

, Material Semimetallic NAO
Rod-Like Rod-Like Form Dry Mix Particles Dry Mix Particles Breaking Load 2.9 5.7 1.0 17.7 pounds force Standard 1.3 0.5 1.0 2.2 Deviation (N-1) Preforms formed from an equal mixture of the NAO and semimetallic materials demonstrated breaking strengths as shown below.
One Part NAO One PartSemimetallic Mixture Rod-Like Form pry Mix Particles Breaking Load 2.0 12.7 pounds force Standard ~ 1.3 1.6 Deviation (N-1) Example 8 Improyed Rheology of Materials Processed by the Inventions The formulas described in Example 5 were thoroughly mixed in a Littleford blender and a sample of each dry mix was set aside. The remaining material was processed into rod-like particles according to the invention previously described.
Test cups, similar to a drinking cup configuration, 5" tall, 2i" diameter at the base and 3" diameter at the lip were molded from cylindrical preforms 1 7/8" in diameter and 1i" to 2i" high formed from the dry mix sample and the rod-like particles of the semimetallic and NAO materials above. In this cup flow test, the minimum pressure needed to completely fill the mold cavity using the rod-like particles is recorded. Preforms made from QB1\51918.

~ ~~~"lad the conventional dry mix of each material were then molded under identical conditions. The test moldings are then compared between the dry mix and rod-like particle forms of the materials. The results were as follows:
Rod-Like NAO Formula Dry Mix Particles Molding Pressure 500 500 psi Time to mold did not close 53 closure sec.
Final cup height 4.9/4.3 5/5 max./ave. in Rod-Like Semimetallic pry Mix Particles Formula Molding, Pressure 2000 2000 psi Time to mold ~ did not close ' 21 closure sec.
Final cup height 4.1/3.7 5/5 max./ave. in Each composition in the form of rod-like particles produced complete moldings whereas the Littleford dry mixes did not completely fill the mold cavity under identical conditions.
Example 9 Improved Flow Of Rod-Like Particles The following raw materials were thoroughly mixed in a Littleford blender.
QB1~.51918.

, _ Material Ingredient (% Weight) A B

Powdered Phenolic Novolac Binder 8.4 6.1 Liquid Phenolic Resole (PLENCO 12194) 3.0 3.0 Nitrile Rubber 1.5 1.5 Cashew Particles 1.2 1.3 Graphite 13.5 13.5 Petroleum Coke 5.2 5.2 Barium Sulfate 11.2 11.9 Steel Fibers 27.5 28.0 Iron Powder 28.0 29.0 Zinc Stearate 0.5 0.5 A sample of each was set aside and the rest of the material was processed into rod-like particles according to the invention described above.
Circular preforms 1" thick and 1 7/8" in diameter were made from the dry mix of each formula and from the rod-like particles of each formula. These preforms were compression molded, without preheating, under 2000 psi directly on top of a heated steel disk, 2" in diameter and 0.190" thick. This disc back plate had sixteen 1/4"
diameter holes drilled through it. These so called integrally molded (I.M.) holes were equally spaced in a 4 by 4 arrangement. The force required to shear the material from the circular back plate was measured according to the parameters recommended in SAE procedure J840. The results from the molding operation and shear strength testing are shown in the following table.
QB1\51918.

.~28'~~ ~

Material A_ B, rod-like rod-like dry mix particles dry mix particles ~ of back plate <80 100 <10 >90 holes filled Average shear 2303 2496 1005 1772 force, lbs. force Standard 303 318 232 542 Deviation (N-1) Shear failure material material pull out material mode The dry mix and rod-like particles of material A do not significantly differ in terms of shear strength however, the percentage of back plate holes filled is greatly improved by using the rod-like particles. When the resin amount is lowered to 22~ volume the improvement in hole fill and shear strength afforded by the invention is dramatic. Previously, improving the flow of friction materials meant increasing the resin amount in the formula or modifying the molding process. This invention now offers a new and novel approach to improving the flow of these resin starved types of materials.
Example 10 Demonstration of Free Flowing Nature of Rod-Like Particles The dry mix samples from the materials described in Example 5 were charged into the stationary hopper apparatus of an automatic, volumetric, hydraulic preform machine. When the machine was operated, no preforms were obtained as the bulky, dusty dry mix constantly bridged and was unable to consistently flow into the preform cavity.
When rod-like particles of the same dimensions as Example 2 and materials of Example 5 were charged into QB1~.51918.

the hopper apparatus, the particles gravity fed into the preform cavity such that the machine produced regular, cylindrical preforms throughout the test run. Preforms of 350 grams were obtained with a variance of less than 10 grams using this volumetric loading procedure.
Example 11 Transfer Molding of Dry Littleford Mix The dry mix of Example 1 before formation into particles is weighed into 150 gram charges and placed in a pressure preformer operating at 1500 psi where it is pressed to form a cylinder approximately 2 inches high by approximately 2" in diameter. Several preforms of this size were made and placed in the transfer cylinder of a standard ASTM D1896 Transfer Mold maintained at 330°F
used on a 100 ton molding press. The press was closed and 2400 psi applied to the transfer cylinder. After 5 minutes the transfer pressure was relaxed and the press opened. There was observed only slight flow into the gates and runner and no suitable parts were produced.
When the dry mix is placed into the mold without preheating, nearly identical results obtained. This demonstrates the lack of flow of the dry mix either preformed or as produced.
Example 12 Transfer Molding of Rod-Like Particles Particles of the invention obtained from Example 2 were preheated by tumbling in a hot air stream to about 230°F in 2 minutes. The particles were easily charged to a transfer mold for flexural strength bars. The mold was heated to 330°F and a pressure of 2400 psi was applied for 3 minutes. The bars obtained were compared to bars made without preheating. The bars that were made from rod-like particles which had not been preheated did not produce as good appearing flex bars. The unheated rod-QB1151918.

.. . _ ' -25-like particles did flow enough to fill the cavity;
however, there was very little flash on the molded bars as compared to those obtained when the particles were preheated. In addition, some blistering occurred on a few of the bars formed from the non-preheated particles.
Moreover, the high quality surfaces realized on the bars made from the preheated particles were not reproduced when the particles were not preheated. A very smooth surface covered all but 1/4" to 1/2" of the flex bar obtained when the particles were preheated. When the particles were not preheated, the smooth surface only covered 1-2" of the 5" bar. The preheating also improved the production rate, appearances and physical properties of the molded part. This example shows the dramatic effect of the rod-like particle formation process on rheological flow properties.
Example 13 Improved Friction Stability and Fade Resistance of Semimetallic Friction Materials Made by the Invention The semimetallic formula described in Example 5 was blended in a Littleford mixer, processed into dustless rod-like particles according to the invention described in Example 2.
Disc pads suitable for the front disc brakes for 1990 Ford Escort (FMSI #D-257) prepared according to the invention and were subjected to an inertia dynomometer test procedure. The dynomometer test measures the brake line pressures required to stop a rotating mass according to the schedule shown below:
A04D Dynomometer Test Procedure:
Brake Type: Ford Escort Disc Actual Wheel Loadings (lbs.): 1013 Rolling Radius (in.): 10.57 Actual inertia (slug ft. ~2): 24.305 QBI\51918.

' -26-C cle Number of Braking Decel Initial St_ ops S eed ~(fpsp~ Rotor m h Temp .
( FBI

Instrument 10 30 10 250 Check Stops Pre-Burnish 4 30 5,10,20,30 250 Effectiveness Stops 4 60 5,10,20,30 250 Burnish Stops 100 30 10 300 Post Burnish 4 30 5,10,20,30 250 Effectiveness Stops 4 60 5,10,20,30 250 Baseline Stops 3 30 10 250 Fade Stops 12 60 15 250-700 Recovery Stops 5 30 10 --Post Fade/Recovery 4 30 5,10,20,30 250 Effectiveness Stops 4 60 5,10,20,30 250 Pad Inspection -- -- -- --600F Wear Stops 75 60 12 600 Pad Inspection -- -- -- --800F Wear Stops 50 60 12 800 Post Wear Tests 4 30 5,10,20,30 250 Effectiveness Stops 4 60 5,10,20,30 250 The results from de and covery portions of the fa re the test on brake in accord ance with he pads made t invention are shown in Table1 below.

QB1\51918.

Table 1 Baseline Fade Recoverv StOjJ Initial Line Initial Line Initial Line No. Rotor Pressure Rotor Pressure Rotor Pressure Temp_ psi Tempi psi Temp- psi.

'F

Brake pads molded from the conventional dry mix form of the friction material were similarly tested according to the A04D inertia dynomometer schedule. The results from the fade portion of the test are shown in Table 2 below.
QB1\51918.

~~~~~e~~

Table 2 Baseline Fade Recovery StOb Initial Line Initial Line Initial Line No. Rotor Pressure Rotor Pressure Rotor Pressure Temp psi Temp- psi Temp- si.

'F ~F

From these results it may be concluded that semimetallic friction materials molded from the rod-like particles possess improved frictional stability and fade resistance in comparison to friction materials molded from a dry mix of the same composition.
Example 14 Improved Molding of Non-Asbestos Organic Friction Materials Made by the Invention Cam and Anchor friction elements for class 8 truck air brake systems (FMSI #4515) were prepared in the conventional manner from the following ingredients:
QBt\51918.

~ .
' -29-~ weight material Ac Bc Powdered Phenolic Novolac Binder 17 13 Nitrile Rubber & Cure Agents 3 4 Rubber Scrap (-20 mesh) 12 5 Fiber Glass g.6 -Mineral Fibers - 23 Graphite 7,3 7 Petroleum Coke 4 3 Copper Powder - 12 Barium Sulfate 30 26 Aluminum Oxide 1.5 1.2 Marble White 2.6 -Vermiculite 11 2.8 Acrylic Pulp (processing aid) 2.5 2.5 Zinc Stearate (mold release) 0.5 0.5 The above ingredients were thoroughly mixed in a Littleford blender. Preforms in the near.net shape of the final element were formed under 2000 psi for 10 seconds at room temperature. It is necessary to use pulps of organic polymers as processing aids to obtain quality preforms of the dry mix. The preforms were then placed into a mold cavity preheated to 300°F and molded under 2000 psi for 15 minutes.
To obtain blister free moldings from the dry mix preforms, the press was opened and closed many times during the molding process. In this case, the mold was opened after 1 minute, and closed after 15 seconds.
After 30 seconds the mold was reopened for 15 seconds and closed after another 3o seconds. The mold was breathed in this way through 8 minutes of molding to allow enough vapors to escape so a solid, infusible element was ejected from the mold after 15 minutes.
Cam and anchor 4515 friction elements were prepared from identical formulas of Ac and Bc above that had been processed into rod-like particles according to the QB1~51918.

' -30-invention of Example 2. The only difference in the formulas being that a portion of the powdered novolac binder was replaced by PLENCO 12194, and, as no preforming in required, the organic pulp processing aid is omitted from the formula. The rod-like particles of the invention were preheated to about 220°F with 280°F, 60 cfm air in 4 minutes. The preheated particles were easily charged into the mold cavity and pressure was applied. Due to the uniform preheat, press breathing was not required and solid infusible elements were ejected from the mold in 5 minutes.
Example 15 Improved Wear Resistance of Non-asbestos Organic Friction Materials Made by the Invention Disc brake pads suitable for a Ford F-250 pickup truck (FMSI #D-120) were prepared from a sample of the Littleford dry mix and the rod-like particle form of the NAO formula described in Example 5. The friction materials were tested according to the A04D inertia dynomometer schedule described in Example 13.
Frictional properties between the two material forms proved to be nearly identical. The only noticeable difference in frictional performance between the two material forms came during the 800°F wear cycle when the brake pads made from rod-like particles demonstrated a 20~ higher coefficient of friction than the brake pads made from the composition's dry mix. The friction material's wear resistance was dramatically improved as the following table indicates:
QB1\51918.

' -31-Total Brake Pad Wear After A04D
Dvnomometer Test Procedure NAO Form. inches Lost Grams Lost Dry Mix .171 91.5 Rod-Like Particles .134 7g.2 Example 16 Improved Method for the Dispersal of Friction and Wear Controlling Particles Disc brake pads were molded by combining various l0 proportions of the rod-like particles of the non-asbestos organic and semimetallic materials described in Example 5.
The two different friction materials were combined in the following weight percents:
Trial # NAO % Semimetallic Physical property tests on the 0, 50, and 100 percent semimetallic materials gave the following results:
~ Semimetallic Material Physical Property 0 50 100 Specific Gravity 2.89 3.05 3.16 Flexural @ 25C psi 4580 4445 3987 Flexural @ 150C psi 2626 2959 3251 Modulus 25C psi 1.2E6 l.lE6 9.3E5 @

Modulus @ 150C psi 6.8E5 6.5E5 7.8E5 QBI\51918.

' -32-Shear Strength @ 25°C psi 6823 6125 5073 A friction material test machine commonly referred to as a CHASE machine, was used to evaluate the friction and wear properties of these materials. The machine was operated in the constant output or constant friction force mode. The sample was applied for 20 seconds and lifted for 10 seconds for 150 applications at 450°F with a drum speed of 420 rpm. The samples were required to produce 100 pounds of friction force during the application. The following table lists the results from this test.
Semimetallic 450° Wear Test Property 0 30 50 70 100 Friction Coefficient .44 .31 .38 .29 .30 Thickness loss .021 .006 .013 .007 .006 Thickness Loss ~ 1.20 1.01 1:02 1.14 0.88 ~ Weight Loss Another CHASE test protocol referred to as the GM
R60 test was used to study the high speed, high temperature characteristics of these materials. While the 100 percent non-asbestos organic material faded dramatically during the high speed, high temperature fades of the test, each of the above samples made with semimetallic rod-like particles demonstrated consistent friction levels throughout the test. The wear resistance was also improved with the use of the semimetallic materials.
D-120 brake pads were prepared from the NAO's dry mix, and from rod-like particles formed from the dry mix.
Similar brake pads were made from a 70% NAO, 30%
semimetallic blend of their dry mixes, and from a 70~
NAO, 30~ semimetallic blend of the rod-like particles.
The brake pads were subjected to the A04D dynomometer test procedure previously described. The results from QB1\51918.

the high temperature portions of the test are shown in the following table.
Brake Line Pressure 70~ NA0:30%
Semimetallic Fade Initial NAO Dry Mix Rod-Like NAO

StOIJ Rotor Drv Rod-Like Particles No. hemp- Mix Particles (Approx~

Recovery stop #1 750 379-799 420-725 443-703 428-677 Average .034 .033 .035 .035 inches lost during Fade cycle Average inches .077 .077 .106 .022 lost during 800°
wear cycle From these results it may be concluded that the high temperature performance of friction materials may be improved by the use of semimetallic materials in the form of rod-like particles. Improvements may be realized when the semimetallic is added at only 30~ by weight.
QB1~51918.

2.
i . ..

Example 17 Improved Performance Offered by the Invention The ingredients listed below were charged into a Littleford blender and mixed for 20 minutes.

Ingredient ~ by Weigrht Powdered Phenolic Novolac Binder 14.0 Liquid Resole (PLENCO 12194) 2.0 Nitrile Rubber 3.0 Rubber Cure System 0.1 Glass Fiber 13.5 Graphite g.3 Petroleum Coke 4.5 Ground Scrap Rubber 12.1 BaS04 29.5 Kyanite 1.5 Calcium Carbonate 2.5 Vermiculite g.0 Zinc Stearate , 0.5 A sample of the dry mix was set aside and the remaining material converted into rod-like particles according to the invention as described in Example 2.
D-120 brake pads were molded from the combinations shown in the following table.
Material No. Above NAO Semimetallic from Example 5 1 100 dry mix 0~
2 50~ dry mix 50~ dry mix 3 50~ rod-like particles 50~ rod-like particles The pads were prepared under identical conditions and subjected to the A04D dynomometer test procedure previously described.
Results from the dynomometer tests are shown in the following table:
QBI\51918.

' _ 2.~2~°~~

Brake Line Pressure Fade Stop Initial Material No. Rotor Temp.

(Approx. F~

Recovery 750 919-1338 658-1035 551-821 Stop No. 1 Total Pad 0.123 0.142 0.108 Thickness Loss in From these results it may be concluded that the high temperature performance of NAO friction materials may be improved with the use of rod-like particles of semimetallic friction materials. Simply blending portions of NAO and semimetallic dry mixes does not improve performance as well as blending rod-like particles.
It will be apparent to those skilled in the art that a number of modifications and changes can be made without departing from the spirit and scope of the present invention.
QB1~51918.

Claims

1. A method of preparing a friction element comprising:

a) forming cylindrical rod-like particles of a material comprising a mixture of friction ingredients, a solid thermosetting resin and an effective amount of a liquid agent which maintains the temperature during rod-like particle formation below the curing temperature of the solid resin, said rod-like particles having a diameter of about 3/32" to about 1/4";

b) preheating said rod-like particles;

c) introducing a predetermined amount of said rod-like particles into a friction element mold; and d) forming a friction element by compressing the rod-like particles under heat and pressure until the resin has become infusible.

2. The method of claim 1 in which the rod-like particles are formed in a pellet mill.

3. The method of claim 1 in which the liquid agent is a liquid phenolic resole characterized as the reaction product of phenol and formaldehyde.

4. The method of claim 1 in which the rod-like particles have a diameter to length ratio greater than 0.25 and contain no more than 15% by weight of material smaller than 60 mesh.

5. The method of claim 1 in which the particles are preheated by a stream of hot gas.

6. The method of claim 1 in which the rod-like particles are formed into a friction element by compressing them under heat and pressure and maintaining them at a temperature above about 250°F and under a pressure greater than about 80 psi.

7. A friction element produced by the method of claim 1.

8. Substantially dust-free, rod-like particles having a diameter of about 3/32" to about 1/4" and a length of about 1/8" to about 1", said rod-like particles being of a composition comprising about 5% to about 30% by weight of a thermosetting binder resin; and about 1% to about 50%
by weight of a temperature controlling agent capable of lowering the temperature of the materials during particle formation.

9. The particles of claim 8, wherein said composition further comprises about 5% to about 50% by weight of reinforcing fillers; about 0% to about 60% by weight of organic fillers; and about 5% to about 80% by weight of inorganic fillers.

10. A composition for forming rod-like particles of friction ingredients, said composition comprising about 5% to about 30% by weight of a thermosetting resin and about 1% to about 50% by weight of a temperature controlling agent which keeps the temperature of the composition below the curing temperature of the resin when the composition is being formed in a pellet mill into rod-like particles.

11. The composition of claim 10 further comprising about 5% to about 50 % by weight of reinforcing fillers; about 5% to about 60% by weight of organic fillers; and about 5% to about 80% by weight of inorganic fillers.

12. A composition of claim 10 in which the agent is a liquid phenolic resole characterized as the reaction product of phenol and formaldehyde.

13. A method of preparing a friction element comprising:
a) forming cylindrical, rod-like particles of an uncured mix of friction ingredients, a solid thermosetting resin and an effective amount of liquid phenolic resin which maintains the temperature of the particle formation process below the curing temperature of the solid resin, said rod-like particles having a diameter of about 3/32" to about 1/4";
b) preheating said rod-like particles; and c) molding the preheated rod-like particles into a friction element.

14. A method of claim 13 in which the molding is accomplished by transfer molding.

15. Friction elements manufactured from different types of friction ingredients where the cylindrical rod-like particles of claim 1 prepared from at least one formula are added to a friction element mix which has not been formed into rod-like particles.

16. Friction elements manufactured from different types of friction ingredients where mixtures of rod-like particles of at least two different friction material formulae are preheated and molded together, each friction material formula comprising a mixture of friction ingredients, a solid thermosetting resin and an effective amount of a liquid agent which maintains the temperature during rod-like particle formation below the curing temperature of the solid resin, said rod-like particles having a diameter of about 3/32" to about 1/4".