EP2788533A1 - Method of manufacture a sliding bearing - Google Patents
Method of manufacture a sliding bearingInfo
- Publication number
- EP2788533A1 EP2788533A1 EP12806626.3A EP12806626A EP2788533A1 EP 2788533 A1 EP2788533 A1 EP 2788533A1 EP 12806626 A EP12806626 A EP 12806626A EP 2788533 A1 EP2788533 A1 EP 2788533A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bias portion
- cathodic
- bias
- sliding bearing
- electrolyte
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 230000001965 increasing effect Effects 0.000 claims description 4
- PGGZKNHTKRUCJS-UHFFFAOYSA-N methanesulfonic acid;tin Chemical compound [Sn].CS(O)(=O)=O PGGZKNHTKRUCJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052580 B4C Inorganic materials 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000009713 electroplating Methods 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910019802 NbC Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/10—Bearings
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
Definitions
- the present invention relates to a method of electroplating a sliding bearing with a composite layer of hard particulate incorporated in a metallic matrix, and more particularly, but not exclusively, to bearing shells and thrust washers.
- Bearing shells for journaled engine bearings typically comprises a strong steel backing layer, a lining layer and an overlay layer that provides the running surface for the journaled shaft, e.g. a hollow generally semi-cylindrical steel backing layer, a copper-based alloy lining layer, and a tin, tin-based alloy or composite overlay layer on the inner surface.
- a particular challenge to bearing overlay layer performance is provided by the configuration of vehicle engines to save fuel by using a stop-start operation, in which the engine is stopped each time the vehicle stops, in contrast to conventional engine operation, in which the engine is kept running throughout a vehicle's journey.
- Engines configured for stop-start operation may restart their engines more than one hundred times more frequently than conventionally configured engines running continuously throughout each vehicle journey.
- the particular problem that an engine configured for stop- start operation presents arises because engine bearings are conventionally hydrodynamically lubricated, with little or no lubrication initially being provided to the bearings when the engine starts, leading to particularly significant wear during the start-up phase.
- a method of manufacturing a sliding bearing comprising providing a substrate as a cathode in an electrolyte within which a hard particulate is suspended, and depositing a composite layer of hard particulate embedded in a metallic matrix by applying a repeating cycle of bias pulses to the substrate wherein each cycle comprises a high cathodic bias portion and a further bias portion selected from the group consisting of a low cathodic bias portion, a zero cathodic bias portion and an anodic bias portion.
- a sliding bearing manufactured according to the method of the first aspect.
- an engine comprising a sliding bearing manufactured according to the first aspect.
- the method may further comprise agitating the electrolyte to maintain the hard particulate in suspension.
- the further bias portion may be a low cathodic bias portion.
- the high cathodic bias portion may have a bias of at least 125 % of the low cathodic bias portion.
- the further bias portion may be a zero cathodic bias portion.
- the further bias portion may be an anodic bias portion.
- the absolute value of the anodic bias portion may be between 0.25 and 3.0 times the absolute value of the high cathodic bias portion (i.e. between 0.25 and 3.0 times the magnitude, but of opposite polarity).
- the repeating cycle may have a sawtooth profile in which each cycle comprises a monotonically increasing cathodic bias.
- the pulse cycle may have a length of 5 to 200 ms, and preferably of 10 to 100 ms.
- the high cathodic bias portion may consist of 10 to 95% of the pulse cycle.
- the high cathodic bias portion may have a peak current density of 0.5 to 10 A/dm 2 .
- the mean average cathodic current density of the cycle is lower than 5 A/dm 2 .
- the hard particulate may be selected from the group consisting of TiCN, SiC, NbC, Si 3 N 4 , Al 2 0 3 , TiN, and B 4 C.
- the suspension may comprise 20 to 200 g hard particulate per litre of electrolyte, and preferably 40 to 100 g per litre.
- the metallic matrix may be a pure metal, apart from incidental impurities.
- the metallic matrix may be pure Sn, apart from incidental impurities.
- the metallic matrix may be a metal alloy, apart from incidental impurities.
- the metallic matrix may be a Sn-based alloy, apart from incidental impurities.
- the electrolyte may be a tin methanesulfonic acid electrolyte.
- the electrolyte may comprise 15 to 80 g/l Sn.
- the electrolyte may comprise brightener.
- the sliding bearing may be a bearing shell or a thrust washer.
- Figure 1 shows a schematic illustration of a bearing shell
- Figure 3 shows an SEM micrograph of a section of a sliding bearing having an overlay with a B 4 C hard particulate incorporated into a Sn metallic matrix; and • Figure 4 shows a second bias pulse profile; and
- Figure 1 illustrates a hollow generally semi-cylindrical bearing shell 1 having a steel backing layer 2, a copper-based alloy lining layer 3, a nickel or cobalt diffusion barrier 4, and a composite overlay layer 5 of hard particulate incorporated into a Sn matrix.
- the bearing shell onto which the composite layer is deposited is provided as a cathode in a bath containing a suspension of hard particulate in an electroplating electrolyte, with an anode formed of a material corresponding to the metallic matrix, e.g. a high purity tin anode.
- the electrolyte is a lead-free, tin methanesulfonic acid (MSA) electrolyte (tin ions in methanesulfonic acid), which may comprise performance enhancing additives, such as brightener and anti-foaming agent.
- MSA tin methanesulfonic acid
- performance enhancing additives such as brightener and anti-foaming agent.
- the electrolyte may be the Bright Tin GBF 30 acidic electrolyte system from Schlotter® Galvanotechnik, which uses a reci pe of Schlotter' s ingredients consisting of 13.0 litres Tin Concentrate FS 20 (which contains 310 g/l tin(ll)), 6.0 litres GBF 31 Starter (20 to 25 %wt 2-naptholpolyglycolether, 1 to 2.5 %wt 1 ,2- dihydroxybenzene, and 1 to 2.5 %wt methacrylic acid), 0.4 litres GBR 32 Brightener (35 to 50 %wt 2-isopropoxyethanol, and 5 to 10 %wt 4-phenylbut-3-en-2-one), 1 1.0 litres GBF 33 Make Up Concentrate (which is 45 %wt MSA), and the balance to 100 litres of deionised water.
- Tin Concentrate FS 20 which contains 310 g/l tin(ll)
- GBF 31 Starter (20 to 25 %w
- the suspension is maintained at a temperature of 20 to 30 °C.
- the chemical composition and pH is maintained during deposition by replenishment of the consumed chemicals.
- Hard particulate such as boron carbide, alumina, silicon nitride, boron nitride, silicon carbide, niobium carbide, titanium nitride, or titanium carbo-nitride, with a particle size of less than 7 ⁇ , is suspended in the solution with a concentration of approximately 60 g/l (operation has been demonstrated with 20 to 200 g/l hard particulate, and preferably 40 to 70 g/l). Ultrasonic and/or mechanical stirring agitation is used to maintain the hard particulate in suspension.
- a cathodic bias i.e. a negative bias is applied to the cathode relative to the anode
- creates a cathodic current i.e.
- the cathode bias is cyclically pulsed at with a pulse cycle period of 10 to 20 ms (although operation has been demonstrated with a pulse cycle period of 10 to 40 ms).
- the peak cathodic current density is between 0.5 and 5.0 A/dm 2 , and the mean average current density across the pulse cycle is up to 3.6 A/dm 2 .
- a bias pulse cycle is used having a high cathodic bias V H pulse portion ti and a zero cathodic bias V 0 portion t 2 .
- the high cathodic bias portion is applied for up to 95 % of the pulse cycle (preferably between 10 and 95 %), and produces a high cathodic current density.
- Figure 3 illustrates a sectional view of such a layer, in which the hard particulate 6 appear as dark specks in the metallic matrix of the overlay layer 5.
- the rate of metallic matrix deposition under a constant cathodic current is limited by the ionic mobility of the metal ions (e.g. tin ions), due to the presence of a depletion region in the electrolyte, against the cathode surface.
- the metal ions e.g. tin ions
- hard particulate from the suspension adheres onto the surface, slow deposition of the metal ions that occurs under constant cathodic current is inefficient at incorporating the surface particles into the deposited layer, with the particles instead remaining on the surface as the metallic matrix layer grows.
- the concentration of metal ions close to the cathode surface is able to increase, leading to a rapid burst of deposition occurring during the high cathodic bias portions, which increases the efficiency of incorporation of the hard particulate into the deposited layer.
- the pulse cycle may have an alternating high cathodic bias V H portions and low cathodic bias V L portions t 2 '.
- the high cathodic bias V H is at least 1.25 times greater than the low cathodic bias V L .
- a zero cathodic bias portion also known as off-time, for example following the high cathodic bias portion.
- a double polarity pulse cycle may be used, in which an anodic bias pulse portion (i.e. a reverse bias, relative to the cathodic bias) may be provided.
- the pulse cycle may have high cathodic bias V H pulse portion V, an anodic bias V R pulse portion t 2 ", a zero cathodic bias V 0 portion t 3 ", and a low cathodic bias V L portion t 4 ".
- the anodic bias portion has a bias that is between -0.25 and - 3.0 times the bias of the high cathodic bias portion (i.e. its magnitude is between 0.25 and 3.0 times the magnitude, but of opposite polarity).
- Such anodic bias pulses may de-plate metal ions from the deposited layer, providing a high concentration of ions close to the cathode surface, further increasing the subsequent rate of deposition during the high cathodic bias pulse portion, further enhancing the incorporation of hard particulate into the deposited layer of metallic matrix.
- the sliding bearing may be a bearing lining or a thrust washer, which is inserted into the bearing assembly of an engine.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Sliding-Contact Bearings (AREA)
- Electroplating Methods And Accessories (AREA)
- Shafts, Cranks, Connecting Bars, And Related Bearings (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A method of manufacturing a sliding bearing comprising providing a substrate as a cathode in an electrolyte within which a hard particulate is suspended, and depositing a composite layer of hard particulate embedded in a metallic matrix by applying a repeating cycle of bias pulses to the substrate wherein each cycle comprises a high cathodic bias portion and a further bias portion selected from the group consisting of a low cathodic bias portion, a zero cathodic bias portion and an anodic bias portion, and a sliding bearing manufactured by such a method.
Description
METHOD OF MANUFACTURE A SLIDING BEARING
The present invention relates to a method of electroplating a sliding bearing with a composite layer of hard particulate incorporated in a metallic matrix, and more particularly, but not exclusively, to bearing shells and thrust washers.
BACKGROUND
Bearing shells for journaled engine bearings typically comprises a strong steel backing layer, a lining layer and an overlay layer that provides the running surface for the journaled shaft, e.g. a hollow generally semi-cylindrical steel backing layer, a copper-based alloy lining layer, and a tin, tin-based alloy or composite overlay layer on the inner surface.
It is desirable to provide increased wear resistance and to improve the fatigue strength of layers in bearing linings, particularly overlay layers. A particular challenge to bearing overlay layer performance is provided by the configuration of vehicle engines to save fuel by using a stop-start operation, in which the engine is stopped each time the vehicle stops, in contrast to conventional engine operation, in which the engine is kept running throughout a vehicle's journey. Engines configured for stop-start operation may restart their engines more than one hundred times more frequently than conventionally configured engines running continuously throughout each vehicle journey. The particular problem that an engine configured for stop- start operation presents arises because engine bearings are conventionally hydrodynamically lubricated, with little or no lubrication initially being provided to the bearings when the engine starts, leading to particularly significant wear during the start-up phase.
It has been proposed to increase the wear resistance of engine bearings by the incorporation of hard inorganic particles, which are substantially insoluble in the electroplating electrolyte, into bearing overlay layers. Exemplary materials are the incorporation of aluminium oxide, silicon nitride, silicon carbide or boron carbide hard particulate into a tin-based alloy matrix. However, the production of such composite layers, with a high concentration of hard particulate, is difficult by conventional electroplating techniques, particularly in a tin-based alloy matrix (e.g. at least 50 %wt tin), and most particularly in the case of a pure tin matrix.
SUMMARY OF THE DISCLOSURE
According to a first aspect, there is provided a method of manufacturing a sliding bearing comprising providing a substrate as a cathode in an electrolyte within which a hard particulate is suspended, and depositing a composite layer of hard particulate embedded in a metallic matrix by applying a repeating cycle of bias pulses to the substrate wherein each cycle comprises a high cathodic bias portion and a further bias portion selected from the group consisting of a low cathodic bias portion, a zero cathodic bias portion and an anodic bias portion.
According to a second aspect, there is provided a sliding bearing manufactured according to the method of the first aspect.
According to a third aspect, there is provided an engine comprising a sliding bearing manufactured according to the first aspect.
The method may further comprise agitating the electrolyte to maintain the hard particulate in suspension. The further bias portion may be a low cathodic bias portion.
The high cathodic bias portion may have a bias of at least 125 % of the low cathodic bias portion. The further bias portion may be a zero cathodic bias portion. The further bias portion may be an anodic bias portion.
The absolute value of the anodic bias portion may be between 0.25 and 3.0 times the absolute value of the high cathodic bias portion (i.e. between 0.25 and 3.0 times the magnitude, but of opposite polarity).
The repeating cycle may have a sawtooth profile in which each cycle comprises a monotonically increasing cathodic bias.
The pulse cycle may have a length of 5 to 200 ms, and preferably of 10 to 100 ms.
The high cathodic bias portion may consist of 10 to 95% of the pulse cycle.
The high cathodic bias portion may have a peak current density of 0.5 to 10 A/dm2. The mean average cathodic current density of the cycle is lower than 5 A/dm2.
The hard particulate may be selected from the group consisting of TiCN, SiC, NbC, Si3N4, Al203, TiN, and B4C. The suspension may comprise 20 to 200 g hard particulate per litre of electrolyte, and preferably 40 to 100 g per litre.
The metallic matrix may be a pure metal, apart from incidental impurities. The metallic matrix may be pure Sn, apart from incidental impurities.
The metallic matrix may be a metal alloy, apart from incidental impurities. The metallic matrix may be a Sn-based alloy, apart from incidental impurities.
The electrolyte may be a tin methanesulfonic acid electrolyte. The electrolyte may comprise 15 to 80 g/l Sn. The electrolyte may comprise brightener.
The sliding bearing may be a bearing shell or a thrust washer. BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention are further described hereinafter with reference to the accompanying drawings, in which:
• Figure 1 shows a schematic illustration of a bearing shell;
• Figure 2 shows a first bias pulse profile;
· Figure 3 shows an SEM micrograph of a section of a sliding bearing having an overlay with a B4C hard particulate incorporated into a Sn metallic matrix; and
• Figure 4 shows a second bias pulse profile; and
• Figure 5 shows a third bias pulse profile.
DETAILED DESCRIPTION
Figure 1 illustrates a hollow generally semi-cylindrical bearing shell 1 having a steel backing layer 2, a copper-based alloy lining layer 3, a nickel or cobalt diffusion barrier 4, and a composite overlay layer 5 of hard particulate incorporated into a Sn matrix. The bearing shell onto which the composite layer is deposited is provided as a cathode in a bath containing a suspension of hard particulate in an electroplating electrolyte, with an anode formed of a material corresponding to the metallic matrix, e.g. a high purity tin anode.
The electrolyte is a lead-free, tin methanesulfonic acid (MSA) electrolyte (tin ions in methanesulfonic acid), which may comprise performance enhancing additives, such as brightener and anti-foaming agent. For example the electrolyte may be the Bright Tin GBF 30 acidic electrolyte system from Schlotter® Galvanotechnik, which uses a reci pe of Schlotter' s ingredients consisting of 13.0 litres Tin Concentrate FS 20 (which contains 310 g/l tin(ll)), 6.0 litres GBF 31 Starter (20 to 25 %wt 2-naptholpolyglycolether, 1 to 2.5 %wt 1 ,2- dihydroxybenzene, and 1 to 2.5 %wt methacrylic acid), 0.4 litres GBR 32 Brightener (35 to 50 %wt 2-isopropoxyethanol, and 5 to 10 %wt 4-phenylbut-3-en-2-one), 1 1.0 litres GBF 33 Make Up Concentrate (which is 45 %wt MSA), and the balance to 100 litres of deionised water. This forms a solution of 30 to 60 g/l tin, although concentrations of 15 to 80 g/l may be used. The suspension is maintained at a temperature of 20 to 30 °C. The chemical composition and pH is maintained during deposition by replenishment of the consumed chemicals.
Hard particulate, such as boron carbide, alumina, silicon nitride, boron nitride, silicon carbide, niobium carbide, titanium nitride, or titanium carbo-nitride, with a particle size of less than 7 μηι, is suspended in the solution with a concentration of approximately 60 g/l (operation has been demonstrated with 20 to 200 g/l hard particulate, and preferably 40 to 70 g/l). Ultrasonic and/or mechanical stirring agitation is used to maintain the hard particulate in suspension. A cathodic bias (i.e. a negative bias is applied to the cathode relative to the anode) creates a cathodic current (i.e. a negative current, with respect to the anode) that drives the positively charged tin ions towards the sliding bearing cathode, and deposits the tin ions onto the
cathode surface. To provide an enhanced incorporation of the B4C hard particulate the cathode bias is cyclically pulsed at with a pulse cycle period of 10 to 20 ms (although operation has been demonstrated with a pulse cycle period of 10 to 40 ms). The peak cathodic current density is between 0.5 and 5.0 A/dm2, and the mean average current density across the pulse cycle is up to 3.6 A/dm2.
As illustrated in Figure 2, in one embodiment a bias pulse cycle is used having a high cathodic bias VH pulse portion ti and a zero cathodic bias V0 portion t2. The high cathodic bias portion is applied for up to 95 % of the pulse cycle (preferably between 10 and 95 %), and produces a high cathodic current density.
By using pulsed electroplating, it is possible to uniformly incorporate up to 20 %wt B4C hard particulate into a Sn metallic matrix of a sliding bearing overlay layer. Figure 3 illustrates a sectional view of such a layer, in which the hard particulate 6 appear as dark specks in the metallic matrix of the overlay layer 5.
The rate of metallic matrix deposition under a constant cathodic current is limited by the ionic mobility of the metal ions (e.g. tin ions), due to the presence of a depletion region in the electrolyte, against the cathode surface. Although hard particulate from the suspension adheres onto the surface, slow deposition of the metal ions that occurs under constant cathodic current is inefficient at incorporating the surface particles into the deposited layer, with the particles instead remaining on the surface as the metallic matrix layer grows. In contrast, during the zero cathodic bias portions (and similarly during lower cathodic bias portions or during anodic bias portions), the concentration of metal ions close to the cathode surface is able to increase, leading to a rapid burst of deposition occurring during the high cathodic bias portions, which increases the efficiency of incorporation of the hard particulate into the deposited layer.
Alternatively, as illustrated in Figure 4, the pulse cycle may have an alternating high cathodic bias VH portions and low cathodic bias VL portions t2'. The high cathodic bias VH is at least 1.25 times greater than the low cathodic bias VL. Additionally there may also be a zero cathodic bias portion (also known as off-time), for example following the high cathodic bias portion. In a yet further embodiment, a double polarity pulse cycle may be used, in which an anodic bias pulse portion (i.e. a reverse bias, relative to the cathodic bias) may be provided. For example, as illustrated in Figure 5, the pulse cycle may have high cathodic bias VH pulse
portion V, an anodic bias VR pulse portion t2", a zero cathodic bias V0 portion t3", and a low cathodic bias VL portion t4". The anodic bias portion has a bias that is between -0.25 and - 3.0 times the bias of the high cathodic bias portion (i.e. its magnitude is between 0.25 and 3.0 times the magnitude, but of opposite polarity).
Such anodic bias pulses may de-plate metal ions from the deposited layer, providing a high concentration of ions close to the cathode surface, further increasing the subsequent rate of deposition during the high cathodic bias pulse portion, further enhancing the incorporation of hard particulate into the deposited layer of metallic matrix.
The sliding bearing may be a bearing lining or a thrust washer, which is inserted into the bearing assembly of an engine.
Throughout the description and claims of this specification, the words "comprise" and "contain" and variations of them mean "including but not limited to", and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.
Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.
Claims
A method of manufacturing a sliding bearing comprising
providing a substrate as a cathode in an electrolyte within which a hard particulate is suspended, and
depositing a composite layer of hard particulate embedded in a metallic matrix by applying a repeating cycle of bias pulses to the substrate
wherein each cycle comprises a high cathodic bias portion and a further bias portion selected from the group consisting of a low cathodic bias portion, a zero cathodic bias portion and an anodic bias portion.
A method according to claim 1 , further comprising agitating the electrolyte to maintain the hard particulate in suspension.
A method according to claims 1 or 2, wherein the further bias portion is a low cathodic bias portion.
A method according to claim 3, wherein the high cathodic bias portion has a bias of at least 125 % of the low cathodic bias portion.
A method according to any preceding claim, wherein the further bias portion is a zero cathodic bias portion.
A method according to any preceding claim, wherein the further bias portion is an anodic bias portion.
A method according to claim 6, wherein the absolute value of the anodic bias portion is between 0.25 and 3.0 times the absolute value of the high cathodic bias portion.
8. A method according to any preceding claim, wherein the repeating cycle has a sawtooth profile in which each cycle comprises a monotonically increasing cathodic bias.
9. A method according to any preceding claim, wherein the pulse cycle has a length of 5 to 200 ms.
10. A method according to any preceding claim wherein the high cathodic bias portion consists of 10 to 95% of the pulse cycle.
1 1. A method according to any preceding claim, wherein the high cathodic bias portion has a peak current density of 0.5 to 10 A/dm2.
12. A method according to any preceding claim, wherein the mean average cathodic current density of the cycle is lower than 5 A/dm2.
13. A method according to any preceding claim, wherein the hard particulate is selected from the group consisting of TiCN, SiC, NbC, Si3N4, Al203, TiN, and B4C.
14. A method according to any preceding claim, wherein the suspension comprises 20 to 200 g hard particulate per litre of electrolyte.
15. A method according to any preceding claim, wherein the metallic matrix is a pure metal, apart from incidental impurities.
16. A method according to claim 17, wherein the metallic matrix is pure Sn, apart from incidental impurities.
17. A method according to any one of claims 1 to 14, wherein the metallic matrix is a metal alloy, apart from incidental impurities.
18. A method according to claim 17, wherein the metallic matrix is a Sn-based alloy, apart from incidental impurities.
19. A method according to any preceding claim, wherein the electrolyte is a tin methanesulfonic acid electrolyte.
20. A method according to any preceding claim, wherein the electrolyte comprises 15 to 80 g/l Sn.
21 A method according to any preceding claim, wherein the electrolyte comprises brightener.
22. A method according to any preceding claim, wherein the sliding bearing is a bearing shell or a thrust washer.
23. A sliding bearing manufactured according to the method of any preceding claim.
24. An engine comprising a sliding bearing manufactured according to any preceding claim.
25. A method of manufacturing a sliding bearing substantially as hereinbefore described with reference to the accompanying description and any one of the Figures.
26. A sliding bearing manufactured by the method substantially as hereinbefore described with reference to the accompanying description and any one of the Figures.
27. An engine comprising a sliding bearing manufactured by the method substantially as hereinbefore described with reference to the accompanying description.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1121175.2A GB2497520A (en) | 2011-12-09 | 2011-12-09 | Method of electroplating a bearing surface |
| PCT/GB2012/053037 WO2013083987A1 (en) | 2011-12-09 | 2012-12-06 | Method of manufacture a sliding bearing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2788533A1 true EP2788533A1 (en) | 2014-10-15 |
Family
ID=45541461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP12806626.3A Withdrawn EP2788533A1 (en) | 2011-12-09 | 2012-12-06 | Method of manufacture a sliding bearing |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20140353161A1 (en) |
| EP (1) | EP2788533A1 (en) |
| JP (1) | JP2015501881A (en) |
| CN (1) | CN104105821A (en) |
| BR (1) | BR112014013830A2 (en) |
| GB (1) | GB2497520A (en) |
| WO (1) | WO2013083987A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2529384A (en) * | 2014-06-23 | 2016-02-24 | Daido Metal Co | A plain bearing with composite interplayer |
| GB2535997A (en) * | 2015-02-27 | 2016-09-07 | Daido Metal Co | Composite coating for a plain bearing of an internal combustion engine and method of deposition |
| GB2550953A (en) * | 2016-06-02 | 2017-12-06 | Mahle Int Gmbh | Sliding component and method |
| US11466728B2 (en) | 2018-03-21 | 2022-10-11 | Tenneco Inc. | Bearing and method of manufacturing permitting high temperature heat treatment |
| CN110983393A (en) * | 2019-12-27 | 2020-04-10 | 广东电网有限责任公司电力科学研究院 | Silver-niobium carbide composite coating and preparation method thereof |
| RU2744104C1 (en) * | 2020-06-23 | 2021-03-02 | Российская Федерация, от имени которой выступает ФОНД ПЕРСПЕКТИВНЫХ ИССЛЕДОВАНИЙ | Turbocharger shaft bearings |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1316482C (en) * | 1986-06-30 | 1993-04-20 | Yoshio Shindo | Method for producing a zn-series electroplated steel sheet |
| US6793796B2 (en) * | 1998-10-26 | 2004-09-21 | Novellus Systems, Inc. | Electroplating process for avoiding defects in metal features of integrated circuit devices |
| US20050205425A1 (en) * | 2002-06-25 | 2005-09-22 | Integran Technologies | Process for electroplating metallic and metall matrix composite foils, coatings and microcomponents |
| JP2005530926A (en) * | 2002-06-25 | 2005-10-13 | インテグラン・テクノロジーズ・インコーポレーテッド | Process for electroplating metal and metal matrix composite foils, coatings, and micro components |
| US20040154925A1 (en) * | 2003-02-11 | 2004-08-12 | Podlaha Elizabeth J. | Composite metal and composite metal alloy microstructures |
| EP1616047A1 (en) * | 2003-04-11 | 2006-01-18 | Lynntech, Inc. | Compositions and coatings including quasicrystals |
| JP4812365B2 (en) * | 2005-08-19 | 2011-11-09 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | Tin electroplating solution and tin electroplating method |
| DE102005040151B4 (en) * | 2005-08-25 | 2008-10-09 | Galvotech Dier Gmbh | Process for the electrodeposition of metal layers and mold plate produced by the process |
| CN100516570C (en) * | 2005-12-19 | 2009-07-22 | 广东工业大学 | Composite sliding bearing material and its preparation method |
| DE102006048909A1 (en) * | 2006-10-17 | 2008-04-24 | Robert Bosch Gmbh | Method for galvanically coating a component with a chromium layer used in vehicle construction comprises depositing chromium atoms onto the surface of the component during a cathodic current impulse and further processing |
| US9273932B2 (en) * | 2007-12-06 | 2016-03-01 | Modumetal, Inc. | Method of manufacture of composite armor material |
| ES2694027T3 (en) * | 2007-12-11 | 2018-12-17 | Macdermid Enthone Inc. | Electrolytic deposition of metal-based composite coatings comprising nano-particles |
| US9005420B2 (en) * | 2007-12-20 | 2015-04-14 | Integran Technologies Inc. | Variable property electrodepositing of metallic structures |
| CN102187016A (en) * | 2008-10-17 | 2011-09-14 | 因尼托奈姆股份有限公司 | Method and device for producing low-wear hard coatings |
| US8367217B2 (en) * | 2009-06-02 | 2013-02-05 | Integran Technologies, Inc. | Electrodeposited metallic-materials comprising cobalt on iron-alloy substrates with enhanced fatigue performance |
| CN101613867B (en) * | 2009-07-25 | 2011-05-11 | 天津大学 | Preparation method of electrodeposited Bi2Te3 doped thin film thermoelectric material |
| RU2453640C2 (en) * | 2010-04-15 | 2012-06-20 | Юрий Рэмович Залыгин | Thin-layer ceramic coating, method of making same, friction surface based on thin-layer ceramic coating and method of making same |
| CN102051657A (en) * | 2011-01-21 | 2011-05-11 | 哈尔滨工业大学 | Preparation method of nano Sn/SiC composite plating |
-
2011
- 2011-12-09 GB GB1121175.2A patent/GB2497520A/en not_active Withdrawn
-
2012
- 2012-12-06 US US14/363,990 patent/US20140353161A1/en not_active Abandoned
- 2012-12-06 BR BR112014013830A patent/BR112014013830A2/en not_active Application Discontinuation
- 2012-12-06 EP EP12806626.3A patent/EP2788533A1/en not_active Withdrawn
- 2012-12-06 WO PCT/GB2012/053037 patent/WO2013083987A1/en not_active Ceased
- 2012-12-06 JP JP2014545353A patent/JP2015501881A/en active Pending
- 2012-12-06 CN CN201280060596.3A patent/CN104105821A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2013083987A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112014013830A8 (en) | 2017-06-13 |
| BR112014013830A2 (en) | 2017-06-13 |
| GB2497520A (en) | 2013-06-19 |
| GB201121175D0 (en) | 2012-01-18 |
| CN104105821A (en) | 2014-10-15 |
| WO2013083987A1 (en) | 2013-06-13 |
| US20140353161A1 (en) | 2014-12-04 |
| JP2015501881A (en) | 2015-01-19 |
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