CA2083448A1 - Composite materials resistant to wear and a process for their manufacture - Google Patents
Composite materials resistant to wear and a process for their manufactureInfo
- Publication number
- CA2083448A1 CA2083448A1 CA002083448A CA2083448A CA2083448A1 CA 2083448 A1 CA2083448 A1 CA 2083448A1 CA 002083448 A CA002083448 A CA 002083448A CA 2083448 A CA2083448 A CA 2083448A CA 2083448 A1 CA2083448 A1 CA 2083448A1
- Authority
- CA
- Canada
- Prior art keywords
- particles
- organic
- submicronic
- matrix
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
ABSTRACT OF THE DISCLOSURE
The subject composite materials comprise an association of an organic elastic matrix with a network of non-oxidized quasi spherical particles, of submicronic dimension and of a diameter ranging between 0.1 µm and 10 µm, distributed uniformly in said matrix.
They are intended to coat pieces subjected to the phenomena of wear, erosion, cavitation and abrasion notably in a corrosive medium.
According to a method of manufacture of these composite materials, the non-oxidized submicronic particles are, immediately before their introduction in the organic matrix, plunged into an organic macromolecular dispersant chosen of such type that the macromolecular chains of the dispersant are fixed on the surface of the particles by non-covalent bonds.
The subject composite materials comprise an association of an organic elastic matrix with a network of non-oxidized quasi spherical particles, of submicronic dimension and of a diameter ranging between 0.1 µm and 10 µm, distributed uniformly in said matrix.
They are intended to coat pieces subjected to the phenomena of wear, erosion, cavitation and abrasion notably in a corrosive medium.
According to a method of manufacture of these composite materials, the non-oxidized submicronic particles are, immediately before their introduction in the organic matrix, plunged into an organic macromolecular dispersant chosen of such type that the macromolecular chains of the dispersant are fixed on the surface of the particles by non-covalent bonds.
Description
COMPOSITE M~TERIALS RESISTANT TO F~RICTION 2 0 8 AND A P~OCESS FOR T~lElR M~NUF~CTVRE
The present invention relates to materials resistant to wear as well as to a process for their manufacture.
A number of technological areas have been searched in order to resolve the problems posed by wear, erosion, cavitation and abrasion in corrosive media. These problems are especially important for blades of hydraulic turbines.
Persons in the art have generally sought a material combining the following properties:
-Increased hardness which permits the material to resist the phenomena of erosion and friction;
-Good ductility so as to permit it to resist shocks;
-A structure which assures good behavior against corrosion.
Currently, the materials employed, including steels having high mechanical characterisffcs and ceramics, do not possess all of the above properties which appear to some e~cten~ to be mutually exclusive.
Thus, a material having the requisite durability is not generally very ductile. lf the material is highly resistant to corrosion, it often does not have adequate mechanical properties. The principal problem in the materials which are available today lies in their fragility.
The present invention has for its object the provision of composite materials, easi}y applied to materials which are in current usage, and provides, at the same time, the characteristics of hardness, ductility and an adapatable structure.
Over the course of numerous experiments, the inventors were able to determine that the best results were obtained by associating an organic polymeric matri~ (of elastomeric type, sufficiently elastic to absorb shocks from large suspended particles in a tlowing fluid) with a sufflciently dense network of hard submicronic particles having a nearly spheAcal shape and a regulær distribution. The hard particles are distributed in this organic polymeric matri~c such ~hat, when a particle (for example of some tens of microns by the finest measurement) comes to strike the composite material of the invention~ it is received in a dense bed of hard particles encased in the elastic matrix.
The present invention relates to materials resistant to wear as well as to a process for their manufacture.
A number of technological areas have been searched in order to resolve the problems posed by wear, erosion, cavitation and abrasion in corrosive media. These problems are especially important for blades of hydraulic turbines.
Persons in the art have generally sought a material combining the following properties:
-Increased hardness which permits the material to resist the phenomena of erosion and friction;
-Good ductility so as to permit it to resist shocks;
-A structure which assures good behavior against corrosion.
Currently, the materials employed, including steels having high mechanical characterisffcs and ceramics, do not possess all of the above properties which appear to some e~cten~ to be mutually exclusive.
Thus, a material having the requisite durability is not generally very ductile. lf the material is highly resistant to corrosion, it often does not have adequate mechanical properties. The principal problem in the materials which are available today lies in their fragility.
The present invention has for its object the provision of composite materials, easi}y applied to materials which are in current usage, and provides, at the same time, the characteristics of hardness, ductility and an adapatable structure.
Over the course of numerous experiments, the inventors were able to determine that the best results were obtained by associating an organic polymeric matri~ (of elastomeric type, sufficiently elastic to absorb shocks from large suspended particles in a tlowing fluid) with a sufflciently dense network of hard submicronic particles having a nearly spheAcal shape and a regulær distribution. The hard particles are distributed in this organic polymeric matri~c such ~hat, when a particle (for example of some tens of microns by the finest measurement) comes to strike the composite material of the invention~ it is received in a dense bed of hard particles encased in the elastic matrix.
-2- 2~834~8 The introduction of large particles in organic matrices is already well known and used in the fiel(l of soil embankments for reinforcing such materials against we~ar ca~lsed by walking or motor vehicle traffic on their surface. The materials of this type have been found to be completely unsuitable when they are subjected to the phenomenon of erosion because of tile action of lluids having abrasive particles therein; in this case, in fact, it has been obselved, under the action of ~hese nuids, that the large particles are dislo(lged from the m~trix.
rhe present inventioll therefore relates to, in a first aspect, composite materials comprised of an admixture of an organic elastic matrix with a network of non-oxidized and quasi spherical ceramic particles, of submicronic dimension for the most part and having in gencral a diameter between 0.1 and 10 ~m, distributed uniformly in such matrix~
l`he elastic organic matrix can be chosen from among polyurethane compounds~
~ lternatively, the organic elastic matrix can be chosen from among the synthetic elastomers sucll as butadiene and butyl rubber~
~ he submicronic parties of ceramic non-oxidized powders are chosen from among the carbides, nitrides and carbonitrides of refractory met~ls such as titanium, zirconium, hafnium, tantalum, niobium, tungsten, molybdenum, boron and silicon or a mixture of such metals~
~ ccording to a preferred embodiment, the submicronic particles are chosen ~rom ;llnollg tl~ non-Qxi(lize(l cer~mic powders forme~l belween a metalloid and a refractory me~al, sucll as ~hose ob~ained by the preferred embodiment in the process described in French Patent A-87 0~97 of January 8, 1987. One of the principal advantages of this process is that it enables one to obtain, superficially, a stoichiometric composition within ~% an(l a surface is poor in o~ygen.
I he density of the subrllicronic particles is greater than that of the particles susceptible of causing degradation of the coa~ed material.
l`hey can range between about 16 and about 5, as in the case for example of the particles of WC (d=15.72); TaC (14.48); NbC (7.78); TaN (14.3).
~ or reasons of economy and of optimization of the absorption of shock, there are preferably chosen submicronic particles having a density of about 5.
208~
An important characteristics of the composite materials according to the invent;on is that there does not exist any electrochemicat coupling between the matri~c and the submicronic particles, a couplin~ which would be susceptible of interfering in the eventual corrosion process.
The composite materials according to the invention can be applied on substrates of any nature, such as metal alloys, organic compounds, concre~e, wood, glass and all other composite materials.
The invention also relates eo a process for obtaining these composite n aterials, which enables one to obtain such a perfect distribution of hard submicronic particles in the interior of the matrix as well as the absence of all electrochemical couplings between the matri~c and the particles, avoiding in this way all intervention in the eventual process of corrosion.
According to this process, the uniform and homogeneous distribution, without agglomeration, of submicronic ceramic non-oxidized particles in the matrix is assured by the fact that said submicronic particles are, immediately before their introduction into the matri~c, plunged in an organic macromolecular dispersant chosen such that the macromolecular chains of he dispersant are fixed on the surface of the particles by non-covalent bonds. In this way, the interfacial tension between the organic matrix and the submicronic particles is reduced; on the other hand, the same macromolecular chains assure the maintenance of the distance separating the submicronic particles.
The submicronic particles are thus inserted in the dispersant and a stearic effect is produced by reason of the fact that the sites of the dispersant which are able to accommodate the particles are small in number; the particles will in this way be engulîed at significant distances, in a molecular scale~ one from the other.
The dispersant is preferably chosen from among the polycarboxylic or polysilane compounds or a combination of these two compounds.
According to a preferred embodiment of the invention, the dispersant comprises acombination of a polycarboxylic acid and a polysilo~ane copolymer.
The organic nature of the matrix and of the dispersant assures the polar compatibility of these two components, and permits them to form non-covalent bonds.
Tlle percentage of the submicronic ceramic particles advantageously ranges between 1 and 80% by weight based on the final weight.
~ prncess for tlle manufac~llre of the composite materials according to tl~e invention essentially includes tlle following steps:
-Preparation of the surface of non-oxidi~ed submicronic ceramic powders for insertion ~mdcr ~n agitation less than or equal to 16 000 rpm for about 10 to 30 minutes at a temperature less than 100C in an organic macromolecular dispersant.
-lntroduct;on under agitation less or equal to 16 ~00 rpm and at a temperature less than 100C of ceramic powders prepared in this way in one of the components of tlle organic matrix.
-Introdllction of tlle mi~ture so obtained into the other component of the matrix and the immediate application of the combination on the piece prepared for receiving such material .
crnatively another process for the manufacture of the composite materials according to the invention includes essentially the following steps:
-Prcparation of the surface of ceramic non-o~idized submicronic particles for insertion under agitation less than or equal to 16 000 rpm for 10 to 30 minutes and at a temperatllre less ~han 100C in an organic macromolecular dispersant.
-Intro(lllctioll under agitation less than or equal to 16 000 rpm and at a tcmperatllre less than 100C of ceramic powders so prepared in tlte organic matrix and thc inlllle(liaîe applicatioll of tlle mixtllre on a piece prepared to receive such malerial.
l`lle rapidity of these operations or in the ab~ence thereof, agitation under heat permits one to prevent the eventual phenomenon of the decanting of the particles in the organic matri?~.
11~c process permits the obtaining in a very simple fashion of either solid materials or materials in lamellar layers having a good resistance to erosion.
In t1lis manner an elastic matrix of a density e~ual to 1.1 glcm3~ filled with 30%
by weight of spherical particles of average diameter of 0.7 ~m with a density of 5.4 g/cm3 has a superficial density s)f 5.85 ~ 10 particles per cm2. The shock of a solid particle of 50 llm in diameter on such a surface is absorbed on a surface of about ~ ~ 106 cm2 conlaining 1150 receptive micro-particles.
- 5 - 2~83~8 It can thus be seen that the size of the particles inserted in the elastic matrix is adapted as much to have a sufficient number of particles subjected to the impact as to have specific and important surfaces of particle/matrix bonding, a good adhesion, a good density, and an increased hardness (greater than 2,000 HV (500 g)). On the other hand, the quasi spherical form of the submicronic partic1es is one which best resists the impact of large particles which come and strike the composite material.
The thicknesses of the materials obtained by the preferred embodiment of the process can be very impor~nt (less than or equal to s~veral tens of centimeters) which permits at the time of the impact of the incident particles, the diskibution and the dampening of the shock wave in the mass; in the case of lamellar layers, it will in this way be possible to avoid problems of substratelproduct bonds.
The following e~amples of manufacture of the anti-abrasion composite materials and their application on steel cylinders will pennit one to better understand the present invention, the characteristics which it has and the advantages which it enables one to obtain.
In the examples, the matri~ is a polyurethane matrix but it should be apparent that one of ordinary skill in the art would easily be able to replace this matrix with other elastomeric matrices, in a notable case where it would be necessary to provide matrices having a higher resistance to elevated temperatures.
E~AMPLE 1 l`here was prepared a powder of titanium carbide for use as a reducing agent of calcium carbide prepared in situ in a bath of melted salt essentially comprising calcium chloride, under the conditions described in Example 1 of French Patent A-87 00097.
Ihere is obtained a powder having an mesh of 4.3279 angstroms, wlth a variation of 0.257% and an average granulometry of 0.5 ~m 69.6 g of isocyanate prepolymer (such as that commercially available under the name of DESMODUR ~P-LS 2954 by Bayer), 20.0 g of this powder and 2.0 grams of anorganic dispersant of a base of polycarbox~lic acid-polysiloxane, such as that commercially available under the name BYK P l04 S by BYK-(:hemie (Germany) are mixed with a rotation speed of less than or equal to 1,000 rpm, and then at a rotation - 6- 2~834~8 speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained is added to 8.4 g of a hardener comprising a 67%
solution of a carbonate of propylene of an aromatic substituted diamine.
There is prepared on the other hand steel/chrome cylinders of diameter of 20 mm and a height of 47 mm by cleaning in acetone, drying and treating one of the two surfaces treated with a 100 grain abrasive paper. The treated surfaces are cleaned in acetone and the cylinder dried at 40C. There is applied by the stroke of a brush on the treated surface of the cylinder a layer on the order of 2 to 5 mm of a primary coating of epoxy resin which is dried:
either for 2 hours at 40C: Cylinder A
or for 24 hours at 20C: Cylinder B
It is on these cylinders prepared in this manner that there is immediately applied the material prepared in accordance with Example 1.
E~AMPLE 2 One starts with the powder of titanium carbide prepared under the conditions of Example 1.
59.8 g of isocyanate prepolymer (such as that commercially available under the name DESMODUR VP-LS 2954 by Bayer), 30.0 g of this powder and 3.0 g of an organic dispersant having a polycarbo~ylic acid-polysiloxane base, such as that commercially available under the name of BYK P 104 S by BYK-Chemie (Germany) aremi~ted with an agitation speed less than or equal to 1,000 rpm, and then at a speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained, added to 7.2 g of a hardener comprising 67% solu~ion of a carbonate of propylene of aromatic substituted diamine, is applied immediately on the steel cylinders prepared as described above (A and B).
One starts with a titanium carbide powder prepared under the conditions of Example 1.
~ 7 ~ 2~834~
50.0 g of isocyanate prepo1ymer (such as that commercially available under the name DESMODUR VP-LS 2954 by Bayer), 40.0 g of this powder and 4.0 g of an organic dispersant having a polycarboxylic acid-polysiloxane base, such as that commercially available under the name of BYK P l0~ S by BYK-Chemie (Germany) aremixed with an agi~tion speed less than or equal to l,000 .rpm, and then at a speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained, added to 6 g of a hardener comprising a 67% solution of a substituted aromatic propylene diamine carbonate, is immediately applied on the steel cylinders prepared as mentioned above (A and B).
Besides, there is applied to a cylinder having a layer of primary epoxy coating which is dried for 2 hours at 40C and which is then coated by a mixture comprising 89.3 g of isocyanate prepolymer and the hardening agent utilized in the preceding examples.
The obtained results are as follows:
. ~ _ _ WEAR lN MM FOR DIFFERENT MATERIALS AND UNDER
IDENTICAL CONDlTIONS OF ABRASlVli EROSION
Pu alone 0.50 Pu ~ ceramic 0 20 _ _ Steel charge ino~ austenitic 304 or 0.9 i - I
Steel charge ino~c martenestique Z 0.85 j 05 CN 1~04 I .
Abrasive steel of type 0.7 CREUSABRO (Creusot-Loire) I . _ _ ¦ Construction steel 1.2 Similar results have been obtained by replacing the titanium carbide by titanium nitride or silicon carbide _ _
rhe present inventioll therefore relates to, in a first aspect, composite materials comprised of an admixture of an organic elastic matrix with a network of non-oxidized and quasi spherical ceramic particles, of submicronic dimension for the most part and having in gencral a diameter between 0.1 and 10 ~m, distributed uniformly in such matrix~
l`he elastic organic matrix can be chosen from among polyurethane compounds~
~ lternatively, the organic elastic matrix can be chosen from among the synthetic elastomers sucll as butadiene and butyl rubber~
~ he submicronic parties of ceramic non-oxidized powders are chosen from among the carbides, nitrides and carbonitrides of refractory met~ls such as titanium, zirconium, hafnium, tantalum, niobium, tungsten, molybdenum, boron and silicon or a mixture of such metals~
~ ccording to a preferred embodiment, the submicronic particles are chosen ~rom ;llnollg tl~ non-Qxi(lize(l cer~mic powders forme~l belween a metalloid and a refractory me~al, sucll as ~hose ob~ained by the preferred embodiment in the process described in French Patent A-87 0~97 of January 8, 1987. One of the principal advantages of this process is that it enables one to obtain, superficially, a stoichiometric composition within ~% an(l a surface is poor in o~ygen.
I he density of the subrllicronic particles is greater than that of the particles susceptible of causing degradation of the coa~ed material.
l`hey can range between about 16 and about 5, as in the case for example of the particles of WC (d=15.72); TaC (14.48); NbC (7.78); TaN (14.3).
~ or reasons of economy and of optimization of the absorption of shock, there are preferably chosen submicronic particles having a density of about 5.
208~
An important characteristics of the composite materials according to the invent;on is that there does not exist any electrochemicat coupling between the matri~c and the submicronic particles, a couplin~ which would be susceptible of interfering in the eventual corrosion process.
The composite materials according to the invention can be applied on substrates of any nature, such as metal alloys, organic compounds, concre~e, wood, glass and all other composite materials.
The invention also relates eo a process for obtaining these composite n aterials, which enables one to obtain such a perfect distribution of hard submicronic particles in the interior of the matrix as well as the absence of all electrochemical couplings between the matri~c and the particles, avoiding in this way all intervention in the eventual process of corrosion.
According to this process, the uniform and homogeneous distribution, without agglomeration, of submicronic ceramic non-oxidized particles in the matrix is assured by the fact that said submicronic particles are, immediately before their introduction into the matri~c, plunged in an organic macromolecular dispersant chosen such that the macromolecular chains of he dispersant are fixed on the surface of the particles by non-covalent bonds. In this way, the interfacial tension between the organic matrix and the submicronic particles is reduced; on the other hand, the same macromolecular chains assure the maintenance of the distance separating the submicronic particles.
The submicronic particles are thus inserted in the dispersant and a stearic effect is produced by reason of the fact that the sites of the dispersant which are able to accommodate the particles are small in number; the particles will in this way be engulîed at significant distances, in a molecular scale~ one from the other.
The dispersant is preferably chosen from among the polycarboxylic or polysilane compounds or a combination of these two compounds.
According to a preferred embodiment of the invention, the dispersant comprises acombination of a polycarboxylic acid and a polysilo~ane copolymer.
The organic nature of the matrix and of the dispersant assures the polar compatibility of these two components, and permits them to form non-covalent bonds.
Tlle percentage of the submicronic ceramic particles advantageously ranges between 1 and 80% by weight based on the final weight.
~ prncess for tlle manufac~llre of the composite materials according to tl~e invention essentially includes tlle following steps:
-Preparation of the surface of non-oxidi~ed submicronic ceramic powders for insertion ~mdcr ~n agitation less than or equal to 16 000 rpm for about 10 to 30 minutes at a temperature less than 100C in an organic macromolecular dispersant.
-lntroduct;on under agitation less or equal to 16 ~00 rpm and at a temperature less than 100C of ceramic powders prepared in this way in one of the components of tlle organic matrix.
-Introdllction of tlle mi~ture so obtained into the other component of the matrix and the immediate application of the combination on the piece prepared for receiving such material .
crnatively another process for the manufacture of the composite materials according to the invention includes essentially the following steps:
-Prcparation of the surface of ceramic non-o~idized submicronic particles for insertion under agitation less than or equal to 16 000 rpm for 10 to 30 minutes and at a temperatllre less ~han 100C in an organic macromolecular dispersant.
-Intro(lllctioll under agitation less than or equal to 16 000 rpm and at a tcmperatllre less than 100C of ceramic powders so prepared in tlte organic matrix and thc inlllle(liaîe applicatioll of tlle mixtllre on a piece prepared to receive such malerial.
l`lle rapidity of these operations or in the ab~ence thereof, agitation under heat permits one to prevent the eventual phenomenon of the decanting of the particles in the organic matri?~.
11~c process permits the obtaining in a very simple fashion of either solid materials or materials in lamellar layers having a good resistance to erosion.
In t1lis manner an elastic matrix of a density e~ual to 1.1 glcm3~ filled with 30%
by weight of spherical particles of average diameter of 0.7 ~m with a density of 5.4 g/cm3 has a superficial density s)f 5.85 ~ 10 particles per cm2. The shock of a solid particle of 50 llm in diameter on such a surface is absorbed on a surface of about ~ ~ 106 cm2 conlaining 1150 receptive micro-particles.
- 5 - 2~83~8 It can thus be seen that the size of the particles inserted in the elastic matrix is adapted as much to have a sufficient number of particles subjected to the impact as to have specific and important surfaces of particle/matrix bonding, a good adhesion, a good density, and an increased hardness (greater than 2,000 HV (500 g)). On the other hand, the quasi spherical form of the submicronic partic1es is one which best resists the impact of large particles which come and strike the composite material.
The thicknesses of the materials obtained by the preferred embodiment of the process can be very impor~nt (less than or equal to s~veral tens of centimeters) which permits at the time of the impact of the incident particles, the diskibution and the dampening of the shock wave in the mass; in the case of lamellar layers, it will in this way be possible to avoid problems of substratelproduct bonds.
The following e~amples of manufacture of the anti-abrasion composite materials and their application on steel cylinders will pennit one to better understand the present invention, the characteristics which it has and the advantages which it enables one to obtain.
In the examples, the matri~ is a polyurethane matrix but it should be apparent that one of ordinary skill in the art would easily be able to replace this matrix with other elastomeric matrices, in a notable case where it would be necessary to provide matrices having a higher resistance to elevated temperatures.
E~AMPLE 1 l`here was prepared a powder of titanium carbide for use as a reducing agent of calcium carbide prepared in situ in a bath of melted salt essentially comprising calcium chloride, under the conditions described in Example 1 of French Patent A-87 00097.
Ihere is obtained a powder having an mesh of 4.3279 angstroms, wlth a variation of 0.257% and an average granulometry of 0.5 ~m 69.6 g of isocyanate prepolymer (such as that commercially available under the name of DESMODUR ~P-LS 2954 by Bayer), 20.0 g of this powder and 2.0 grams of anorganic dispersant of a base of polycarbox~lic acid-polysiloxane, such as that commercially available under the name BYK P l04 S by BYK-(:hemie (Germany) are mixed with a rotation speed of less than or equal to 1,000 rpm, and then at a rotation - 6- 2~834~8 speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained is added to 8.4 g of a hardener comprising a 67%
solution of a carbonate of propylene of an aromatic substituted diamine.
There is prepared on the other hand steel/chrome cylinders of diameter of 20 mm and a height of 47 mm by cleaning in acetone, drying and treating one of the two surfaces treated with a 100 grain abrasive paper. The treated surfaces are cleaned in acetone and the cylinder dried at 40C. There is applied by the stroke of a brush on the treated surface of the cylinder a layer on the order of 2 to 5 mm of a primary coating of epoxy resin which is dried:
either for 2 hours at 40C: Cylinder A
or for 24 hours at 20C: Cylinder B
It is on these cylinders prepared in this manner that there is immediately applied the material prepared in accordance with Example 1.
E~AMPLE 2 One starts with the powder of titanium carbide prepared under the conditions of Example 1.
59.8 g of isocyanate prepolymer (such as that commercially available under the name DESMODUR VP-LS 2954 by Bayer), 30.0 g of this powder and 3.0 g of an organic dispersant having a polycarbo~ylic acid-polysiloxane base, such as that commercially available under the name of BYK P 104 S by BYK-Chemie (Germany) aremi~ted with an agitation speed less than or equal to 1,000 rpm, and then at a speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained, added to 7.2 g of a hardener comprising 67% solu~ion of a carbonate of propylene of aromatic substituted diamine, is applied immediately on the steel cylinders prepared as described above (A and B).
One starts with a titanium carbide powder prepared under the conditions of Example 1.
~ 7 ~ 2~834~
50.0 g of isocyanate prepo1ymer (such as that commercially available under the name DESMODUR VP-LS 2954 by Bayer), 40.0 g of this powder and 4.0 g of an organic dispersant having a polycarboxylic acid-polysiloxane base, such as that commercially available under the name of BYK P l0~ S by BYK-Chemie (Germany) aremixed with an agi~tion speed less than or equal to l,000 .rpm, and then at a speed less than or equal to 16,000 rpm, at a temperature on the order of 80C, for 20 minutes.
The mixture thus obtained, added to 6 g of a hardener comprising a 67% solution of a substituted aromatic propylene diamine carbonate, is immediately applied on the steel cylinders prepared as mentioned above (A and B).
Besides, there is applied to a cylinder having a layer of primary epoxy coating which is dried for 2 hours at 40C and which is then coated by a mixture comprising 89.3 g of isocyanate prepolymer and the hardening agent utilized in the preceding examples.
The obtained results are as follows:
. ~ _ _ WEAR lN MM FOR DIFFERENT MATERIALS AND UNDER
IDENTICAL CONDlTIONS OF ABRASlVli EROSION
Pu alone 0.50 Pu ~ ceramic 0 20 _ _ Steel charge ino~ austenitic 304 or 0.9 i - I
Steel charge ino~c martenestique Z 0.85 j 05 CN 1~04 I .
Abrasive steel of type 0.7 CREUSABRO (Creusot-Loire) I . _ _ ¦ Construction steel 1.2 Similar results have been obtained by replacing the titanium carbide by titanium nitride or silicon carbide _ _
Claims (12)
1. A composite material intended for covering pieces subjected to the phenomena of wear, erosion, cavitation and abrasion notably in a corrosive media, characterized in that they are comprised of an association of an elastic organic matrix and a network of quasi spherical non-oxidized ceramic particles, of submicronic dimension for the most part and having in general a diameter ranging between 0.1 µm and 10 µm, distributed uniformly in said matrix, the density of the submicronic particles being between about 16 and about 5.
2. The composite material according to claim 1, characterized in that the organic elastic matrix is chosen from the polyurethanes.
3. The composite material according to claim 1, characterized in that the organic elastic matrix is chosen among the elastomeric organic compounds resistant to temperatures greater than 100°C.
4. Composite materials according to claim 1, characterized in that the submicronic particles are powders of carbides, nitrides or carbonitrides of refractory metals chosen from among titanium, zirconium, hafnium, tantalum, niobium, tungsten, molybdenum, boron and silicon or a mixture of these metal compounds.
5. The composite material according to claim 4, characterized in that the submicronic particles are powders of carbides, nitrides or carbonitrides of known refractory metals.
6. Composite materials according to claim 1, characterized in that the density of the submicronic particles is about 5.
7. Process for the manufacture of composite materials according to claim 1, characterized in that said submicronic particles are, immediately before their introduction into the organic matrix, plunged into a macromolecular organic dispersant chosen of such type that the macromolecular chains of the dispersant are fixed on the surface of the particles by non-covalent bonds.
8. Process of manufacture according to claim 7, characterized in that the dispersant is chosen from among the polycarboxylic or polysilane compounds and combinations of these two compounds.
9. Process of manufacture according to claim 8, characterized in that the dispersant is a combination of a polycarboxylic acid and a polysiloxane copolymer.
10. Process of manufacture according to claim 7, characterized in that the percentage of the filler of submicronic ceramic particles is between about 1 and 80% by weight with respect to the final charge.
11. Process of manufacture according to claim 7, characterized in that it comprises essentially the following steps:
preparation of the surface of non-oxidized submicronic ceramic powders by insertion of such powders, under agitation less than or equal to 16,000 rpm, for about 10 to 30 minutes and a temperature less than 100°C in a macromolecular organic dispersant;
introduction, with agitation less than or equal to 16,000 rpm and a temperature less than 100°C of ceramic powders prepared in this way in one of the component elements of the organic matrix;
introduction of the obtained mixture in the other constituent of the matrix and immediate application of the combination on a piece prepared to receive the coating.
preparation of the surface of non-oxidized submicronic ceramic powders by insertion of such powders, under agitation less than or equal to 16,000 rpm, for about 10 to 30 minutes and a temperature less than 100°C in a macromolecular organic dispersant;
introduction, with agitation less than or equal to 16,000 rpm and a temperature less than 100°C of ceramic powders prepared in this way in one of the component elements of the organic matrix;
introduction of the obtained mixture in the other constituent of the matrix and immediate application of the combination on a piece prepared to receive the coating.
12. Process of manufacture according to claim 7, characterized in that it comprises essentially the following stages:
preparation of the surface of the non-oxidized submicronic ceramic powders by insertion of said powders, under agitation less than or equal to 16,000 rpm, for about 10 to 30 minutes and at a temperature less than 100°C in an organic macromolecular dispersant;
introduction, under agitation less than or equal to 16000 rpm and at a temperature less than 100°C of ceramic powders prepared in this way in the organic matrix and immediate application of the combination on a piece prepared to receive the coating.
preparation of the surface of the non-oxidized submicronic ceramic powders by insertion of said powders, under agitation less than or equal to 16,000 rpm, for about 10 to 30 minutes and at a temperature less than 100°C in an organic macromolecular dispersant;
introduction, under agitation less than or equal to 16000 rpm and at a temperature less than 100°C of ceramic powders prepared in this way in the organic matrix and immediate application of the combination on a piece prepared to receive the coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9114608 | 1991-11-21 | ||
| FR919114608A FR2684105B1 (en) | 1991-11-21 | 1991-11-21 | WEAR RESISTANT COMPOSITE MATERIALS AND PROCESS FOR THEIR MANUFACTURE. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2083448A1 true CA2083448A1 (en) | 1993-05-22 |
Family
ID=9419367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002083448A Abandoned CA2083448A1 (en) | 1991-11-21 | 1992-11-20 | Composite materials resistant to wear and a process for their manufacture |
Country Status (18)
| Country | Link |
|---|---|
| US (2) | US5527849A (en) |
| EP (1) | EP0543753B1 (en) |
| JP (1) | JP3279689B2 (en) |
| KR (1) | KR100241799B1 (en) |
| CN (1) | CN1044610C (en) |
| AT (1) | ATE166370T1 (en) |
| AU (1) | AU658240B2 (en) |
| BR (1) | BR9204446A (en) |
| CA (1) | CA2083448A1 (en) |
| DE (1) | DE69225561T2 (en) |
| DK (1) | DK0543753T3 (en) |
| ES (1) | ES2115659T3 (en) |
| FI (1) | FI925252A (en) |
| FR (1) | FR2684105B1 (en) |
| MX (1) | MX9206625A (en) |
| NO (1) | NO304836B1 (en) |
| TW (1) | TW254965B (en) |
| ZA (1) | ZA929014B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6933331B2 (en) * | 1998-05-22 | 2005-08-23 | Nanoproducts Corporation | Nanotechnology for drug delivery, contrast agents and biomedical implants |
| US5905000A (en) | 1996-09-03 | 1999-05-18 | Nanomaterials Research Corporation | Nanostructured ion conducting solid electrolytes |
| FR2776341B1 (en) | 1998-03-23 | 2000-06-09 | Gec Alsthom Neyrpic | TURBINE WHEEL AND PELTON-TYPE TURBINE EQUIPPED WITH SUCH A WHEEL |
| FR2827869B1 (en) * | 2001-07-26 | 2007-04-13 | Seb Sa | ANTI-ADHESIVE COATING HAVING ENHANCED SCRATCH AND ABRASION RESISTANCE |
| US7708974B2 (en) | 2002-12-10 | 2010-05-04 | Ppg Industries Ohio, Inc. | Tungsten comprising nanomaterials and related nanotechnology |
| FR2877008B1 (en) * | 2004-10-26 | 2007-02-09 | Ccn Soc Par Actions Simplifiee | COMPOSITE MATERIAL COMPRISING AN ORGANIC MATRIX AT LEAST CHARGED WITH NON-OXIDE, QUASI-SPHERICAL PARTICLES AND WITH A PARTICULAR GRANULOMETRY BETWEEN 0.01MU AND 4MU |
| DE102011005921A1 (en) | 2010-12-07 | 2012-06-14 | Aktiebolaget Skf | Friction-increasing paint and thus coated machine part |
| CN106398085A (en) * | 2016-09-09 | 2017-02-15 | 博硕科技(江西)有限公司 | Scratching-resistant halogen-free flame-retardant TPE injection molding material and preparation method thereof |
| CN111454576B (en) * | 2020-05-07 | 2021-10-01 | 北京宇航系统工程研究所 | SiAlCN ceramic precursor modified polyurethane rubber and preparation method and application thereof |
| CN111748272A (en) * | 2020-07-08 | 2020-10-09 | 黄海千 | Preparation method of high cavitation erosion resistance coating |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3560487A (en) * | 1968-04-27 | 1971-02-02 | Hoechst Ag | 17-beta-lactones of 14-beta-hydroxy-steroids and process for preparing them |
| US3780080A (en) * | 1971-05-17 | 1973-12-18 | Gen Electric | Silyl maleates and polysiloxane maleates |
| US4042559A (en) * | 1972-03-23 | 1977-08-16 | The Carborundum Company | Abrasion resistant coated abrasive pipe lining sheet |
| US3876608A (en) * | 1972-05-26 | 1975-04-08 | Du Pont | Thermoplastic films containing spherical inorganic particles of 2 to 10 micron size |
| US3954694A (en) * | 1975-02-03 | 1976-05-04 | Rexnord, Inc. | Wearing composition |
| US4551496A (en) * | 1984-04-11 | 1985-11-05 | General Electric Company | Thermoplastic molding of sinterable silicon carbide |
| JPS62154230A (en) * | 1985-12-26 | 1987-07-09 | Hitachi Maxell Ltd | Magnetic recording medium |
| JPS6335887A (en) * | 1986-07-30 | 1988-02-16 | 東レ株式会社 | Coating fabric |
| US5205971A (en) * | 1988-06-06 | 1993-04-27 | The Dow Chemical Company | Manufacture of non-whiteware ceramic articles |
| JP2821897B2 (en) * | 1989-02-07 | 1998-11-05 | 荒川化学工業株式会社 | Surface sizing agent |
| JPH02260546A (en) * | 1989-03-31 | 1990-10-23 | Toshiba Chem Corp | Semiconductor device |
| JPH02262346A (en) * | 1989-04-03 | 1990-10-25 | Toshiba Chem Corp | Semiconductor device |
| EP0444475B1 (en) * | 1990-02-21 | 1994-04-27 | BASF Aktiengesellschaft | Thermoplastic composition for the preparation of ceramic moulding masses |
| US5194480A (en) * | 1991-05-24 | 1993-03-16 | W. R. Grace & Co.-Conn. | Thermally conductive elastomer |
-
1991
- 1991-11-21 FR FR919114608A patent/FR2684105B1/en not_active Expired - Fee Related
-
1992
- 1992-11-18 MX MX9206625A patent/MX9206625A/en unknown
- 1992-11-18 BR BR929204446A patent/BR9204446A/en not_active IP Right Cessation
- 1992-11-19 NO NO924463A patent/NO304836B1/en not_active IP Right Cessation
- 1992-11-19 FI FI925252A patent/FI925252A/en unknown
- 1992-11-20 ES ES92420430T patent/ES2115659T3/en not_active Expired - Lifetime
- 1992-11-20 DK DK92420430T patent/DK0543753T3/en active
- 1992-11-20 CA CA002083448A patent/CA2083448A1/en not_active Abandoned
- 1992-11-20 JP JP33502992A patent/JP3279689B2/en not_active Expired - Fee Related
- 1992-11-20 EP EP92420430A patent/EP0543753B1/en not_active Expired - Lifetime
- 1992-11-20 AT AT92420430T patent/ATE166370T1/en not_active IP Right Cessation
- 1992-11-20 DE DE69225561T patent/DE69225561T2/en not_active Expired - Fee Related
- 1992-11-20 ZA ZA929014A patent/ZA929014B/en unknown
- 1992-11-20 AU AU28514/92A patent/AU658240B2/en not_active Ceased
- 1992-11-21 KR KR1019920021992A patent/KR100241799B1/en not_active IP Right Cessation
- 1992-11-21 CN CN92112869A patent/CN1044610C/en not_active Expired - Lifetime
- 1992-11-23 US US07/980,210 patent/US5527849A/en not_active Expired - Fee Related
-
1993
- 1993-02-05 TW TW082100794A patent/TW254965B/en active
-
1995
- 1995-12-11 US US08/570,336 patent/US5665807A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3279689B2 (en) | 2002-04-30 |
| ATE166370T1 (en) | 1998-06-15 |
| NO924463D0 (en) | 1992-11-19 |
| KR100241799B1 (en) | 2000-02-01 |
| CN1072424A (en) | 1993-05-26 |
| JPH05239254A (en) | 1993-09-17 |
| DE69225561D1 (en) | 1998-06-25 |
| DE69225561T2 (en) | 1998-11-12 |
| EP0543753A1 (en) | 1993-05-26 |
| DK0543753T3 (en) | 1999-01-18 |
| ES2115659T3 (en) | 1998-07-01 |
| NO304836B1 (en) | 1999-02-22 |
| FR2684105B1 (en) | 1994-09-09 |
| KR930009960A (en) | 1993-06-21 |
| CN1044610C (en) | 1999-08-11 |
| US5527849A (en) | 1996-06-18 |
| FI925252A0 (en) | 1992-11-19 |
| US5665807A (en) | 1997-09-09 |
| AU658240B2 (en) | 1995-04-06 |
| NO924463L (en) | 1993-05-24 |
| FR2684105A1 (en) | 1993-05-28 |
| MX9206625A (en) | 1993-06-01 |
| TW254965B (en) | 1995-08-21 |
| FI925252A (en) | 1993-05-22 |
| AU2851492A (en) | 1993-06-17 |
| ZA929014B (en) | 1993-09-01 |
| EP0543753B1 (en) | 1998-05-20 |
| BR9204446A (en) | 1993-05-25 |
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| EEER | Examination request | ||
| FZDE | Discontinued |