GB2207436A - Solid phase deformation process - Google Patents
Solid phase deformation process Download PDFInfo
- Publication number
- GB2207436A GB2207436A GB08717631A GB8717631A GB2207436A GB 2207436 A GB2207436 A GB 2207436A GB 08717631 A GB08717631 A GB 08717631A GB 8717631 A GB8717631 A GB 8717631A GB 2207436 A GB2207436 A GB 2207436A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyethylene
- pressure
- workpiece
- linear polyethylene
- solid phase
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/30—Drawing through a die
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/475—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pistons, accumulators or press rams
- B29C48/485—Hydrostatic extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/475—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pistons, accumulators or press rams
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/04—Polymers of ethylene
- B29K2023/06—PE, i.e. polyethylene
Abstract
There is disclosed a process for producting a product comprising linear polyethylene which process comprises forming a workpiece which is to be extruded in the solid phase by consolidating under heat and pressure a mass of solid particulate linear polyethylene, subjecting the resulting workpiece to heat treatment under pressure to cause the polyethylene to crystallise in an extended chain morphology with the melting point of the polyethylene being increased to at least 139.5 DEG C and the density to at least 0.98g/cm<3>, and thereafter deforming the workpiece of the resulting polyethylene in the solid phase, for example by passage through a die, to provide the polyethylene product whereby the workpiece is subjected to a deformation ratio of at least 3, and preferably 3 to 25. The resulting polyethylene may have a Youngs modulus of at least 30 GPa and a melting point of at least 139.5 DEG C.
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Description
1 2.c i U "' 4 U' SOLID PHASE DEFORMATION PROCESS This invention relates
to solid phase deformation processes, and more particularly to the sold phase deformation of orientable, semi-crystalline, thermoplastic polymeric materials.
During the past twenty years or so, a &ubstantial amount of research has been carried out into the improvement of mechanical properties of flexible polymers, principally by orientation. The required very high orientation of the molecular chains of flexible polymers, notably linear polyethylene, may be obtained either by preventing the formation of chain-folded crystallites, as with precipitation from solution in an extensional flow regime, or by transforming a previous chain-folded morphology into one comprising extended molecular chains, as occurs using mechanical deformation; see, for example, UK Patent Specifications Nos. 1480479 and 2060469B.
The above-mentioned prior processes produce a high degree of anisotropy in the structure of the polymer, -with concomitant improvement in mechanical properties in the machine direction.
British Patent Specification 2157298A describes and claims a process for the deformation of a workpiece comprising an orientable, thermoplastic polymer by passage in the solid phase through a die having both an entry side and an exit side, which process comprises providing the workpiece comprising the orientable, thermoplastic polymer which is initially present, at least in part, in an extended chain crystalline morphology at the entry side of the die; causing the workpiece to deform in the solid 2 - is 30- phase through the die; and collecting the deformed workpiece from the exit side of the die. This specification indicates that the weight average molecular weight (M W) of polyethylene used in the process may be from 50,000 to 3,000,000. However, it is difficult to process higher molecular weight polyethylene according to -the teaching of this prior specification, especially polyethylene with a MW of greater than 300,000, more particularly greater than 3505000.
The present invention seeks to provide a process comprising a solid phase deformation in which an improvement in mechanical properties - of the polyethylene with more satisfactory processing conditions, and constitutes especially an improvement over the process described in Specification No. 2157298A.
According to the present invention there is provided a process for producing a product comprising linear polyethylene which process comprises forming a workpiece which is to be extruded in the solid phase by consolidating under heat and pressure a mass of solid particulate linear polyethylene, subjecting the resulting workpiece to heat treatment under pressure to cause the polyethylene to crystallise in an extended chain morphology with the melting point of the polyethylene being increased to at least 139.50C and the density to at least 0.98g/cm3. and thereafter deforming a workpiece of the resulting polyethylene in the solid phase, for example by passage through a die, to provide the polyethylene product whereby the workpiece is subjected to a deformation extrusion ratio of at least 3, and preferably 3 to 25.
11 The consolidation under heat and pressure of the mass of solid particulate linear polyethylene is carried out under conditions below the melting point of the polyethylene at the applied pressure with the melting only of a surface layer of the particles to form a solid cohered material. The procedure results in the formation of a solid piece of polyethylene which visually has the appearance of a similar extruded product, but it is an advantage of this procedure that the minimum entanglement occurs between molecules of polyethylene of adjacent particles and this has been found to be important in achieving the benefits provided by this invention.
Preferably the workpiece is formed by consolidating a mass of solid particulate linear polyethylene by compression of as-polymerised polyethylene at ambient temperature using high pressure of the order of 150 to 250, preferably about 200 MPa, and thereafter lowering the pressure to 100 to 160, preferably about 130 MPa; thereafter the compacted powder is heated to a temperature of from 130 to 1500C, and preferably about 1400C, whereby the polyethylene powder is consolidated into a compacted workpiece by melting only a surface layer of the particles to a solid cohered material. The polyethylene of the resulting workpiece is then suitable for annealing to produce the chain extended morphology required by the process of this invention.
Preferably, the deformation effects a reduction in the bulk crosssectional area of the workpiece. (By 'bulk cross-sectional area' is meant the area of the bulk of the workpiece normal to the 4 is machine direction.) This deformation is readily achieved by means of a reducing die. However, deformation in accordance with the invention can be achieved by drawing a workpiece through a pair of opposed pressure rolls.
From a commercial standpoint, the process of the present invention is of particular importance in relation to linear polyethylene having a weight average molecular weight (M W) from 300,000 or 350,000 to 3,000,000, preferably from 350,000 to 1,500,000, and especially from 750.,000 to 1, 000,000.
The term Ilworkpiece" as used herein includes bars, strips, rods, tubes and other cross-sections of solid or hollow stock. The term includes both billets and other forms of stock of greater length; indeed, continuous stock, wbich may be formed as the process is performed, may be utilised.
The workpieces used in the process of this invention may comprise a filler. Examples of useful fibrous fillers include glass, asbestos, metal, carbon and ceramic whiskers, such as ---thoseformed from silicon carbide. Examples of useful laminar fillers include mica, talc and graphite flakes. Chalk and fly ash may also be included. The amount of filler which may advantageously be included depends on the nature of the filler, but up to 50% by weight, preferably from 5 to 30%, especially from 5 to 20% may be incorporated into the polyethylene prior to the consolidation of particles to form a workpiece.
In accordance with a preferred aspect of 1 is pressure extrusior pressure extrusion this invention the workpiece is caused to deform through the reducing die in the solid phase by hydrostatically extruding it therethrough. Draw- assisted hydrostatic extrusion, as described in British Patent Specification No. 1480479, may be utilised with advantage. The net hydrostatic (that is, the.difference between the applied pressure and the applied extrudate for extrusion to occur will, at a given temperature, increase with increasing extrudate pressure and will, at a given extrudate pressure, decrease with increasing temperature. A value from 20 to 300 MPa, preferably from 50 to 200 MPa, for example 100 MPa, is suitable.
The workpiece may also be deformed by drawing it through a heated reducing die without hydrostatic pressure. As the deformation temperature increases (and it may increase to high values where high ambient pressures are used as the melting point of the linear polyethylene increases by approximately 20 0 C for each 100 MPa of a pplied pressure) above 200 0 C process.
difficult. It is, therefore, preferred to employ hydrostatic extrusi6n into an atmospheric pressure with the polyethylene at a temperature from 90 0 C to 1200 C as it undergoes extrusion.
control becomes increasingly While nominal deformation ratios (R N) of up to 50, for example 20, have been obtained with linear polyethylene it is a feature of the process of the present invention that more effective deformation is attained. That is, a given enhancement of a physical property may be attained at a lower deformation ratio by from particulate polyethylene.
the present process starting Accordingly, R N is 1 1 - 6 suitably from 4 to 20, preferably from 8 to 14.
The compacting of the particulate polyethylene may be effected in a separate operation, as is preferred, or may be effected in an extrusion apparatus prior to annealing and deformation, it being understood that the apparatus should preferably be capable of withstanding a pressure of 600 MPa at a temperature of 2600C. Chain-extended crystalline morphology is found to be imparted to the polymer at pressure above 350 MPa (but it is not usually necessary to exceed -480 MPa) and. temperatures above 2200C. It is generally preferr ed 'to produce the chain-extended crystalline morphology at 450 MPa and 2350C.
The presence of. chain-extended crystalline morphology in linear polyethylene is manifest by an increased melting point CDSC) and a higher density: these are, respectively, at least 139.50C or 1400C and at least 0.98 g/cm3.
The invention also provides linear polyethylene prepared by the process of the present invention. This invention further provides oriented linear polyethylene having a weight average molecular weight of at least 350,000, and preferably from 350,000 to 1,000,000 which has been deformed to a deformation ratio of from 3 to 20, and which has a Young's modulus of at least 30 GPa and has a melting point of at least 139.5OC; for example 10, and which has a Young's modulus of at least 30 GPa, for example, of at least 35 GPa.
Furthermore, this invention provides a set hydraulic cementitious or organic thermoset mass is 7 which incorporates a reinforcement constituted by linear polyethylene prepared by the process of the invention. The reinforcement may be in the form of rods, monofilaments, tubes, tapes or the like, and may be non- circular in cross-section.
The invention will now be further illustrated by way of examples with reference to the accompanying drawings, in which:
Figure 1 shows in cross-section high pressure.ann&aling apparatus; and Figure 2 shows in hydrostatic extruder.
cross-section a Referring to Figure 1 there is illustrated high pressure annealing apparatus 1 which comprises an upper cylindrical vessel 2 which is provided with a piston 3 which is provided with a pressure-type seal (not shown) with the surrounding housing. The piston is urged in the downward direction by a ram 4 and a screw-driven universal testing machine (not shown). The entire apparatus as shown in Figure 1 is mounted in the compression zone of the machine. The lower cylindrical vessel 5 constitutes a pressure vessel, the vessel being provided with an end closure 6 which is provided with a central channel 7 to a port 8. The upper vessel 2 and the lower vessel 5 are assembled together in operative position by means of the threaded sections 9 and 10 on the upper and lower vessels 2 and 5, respectively. A cylinder 11 is positioned between the upper and lower vessels 2 and 3. The upper vessel and the pressure vessel are shrouded in separately controlled electrical band heaters 12, 13, which enables a uniform temperature is distribution to be maintained within the pressure vessel. In use a billet of consolidated polyethylene 14 is positioned in the pressure vessel and a silicone fluid 15, such as DC 550 silicone oil, which is introduced into the pressure vessel before fitting the piston 3. Pressurisation of the silicone fluid is achieved by the compressive loading of the piston 3, the lower portion of which is located in the lower vessel during use. The pressure within the pressure vessel is monitored continuously by a foil-gauge pressure transducer (not shown). The transducer is incorporated in. a pressure monitoring pipe which is connected into port 8 using standard high pressure fittings. Thermocouple leads monitoring temperature in the region of the billet pass through the pressurised cylindrical hole in the plug and through the pressure monitoring pipe to an insulated plug (not shown). Because the high temperatures and pressures used in the pressure vessel are severe, the seals 16 around the end closure 6 and the piston 3 employ an 0 ring/mitre ring combination which need frequent replacement. The apparatus shown in Figure 1 was seated on a support stand to enable access for both the thermocouple assembly and the pressure transducer.
PRODUCTION OF WORKPIECE WITH EXTENDED CHAIN MORPHOLOGY A billet of linear produced by polyethylene was a compaction procedure employing as-polymerised linear polyethylene powder (R-516 ex BP Chemicals -Ltd. m W 742,000 and M n 13,600).
The compaction equipment comprised a die and dual ram arrangement, the die itself being shrouded by a controlled band heater which enabled a uniform temperature to be achieved within the cavity of the 1 Q.
r.
die. The as-polymerised polyethylene powder was initially compressed by positioning the die with the powder therein within the compression zone of a 300 tonne hydraulic press. The powder was initially compressed to 200 MPa at the ambient temperature of 200C. The applied pressure was then lowered and maintained at 130 MPa. The band heater around the die was then energized and the heating carried out until after about 40 minutes the polyethylene reached a final equilibrium temperature of 1400C. The pressure and temperature were maintained for a further 10 minute period after which the heater was switched off.. The die. and the contents were cooled by air jets with the 130 MPa pressure being maintained during cooling to ambient temperature. The product formed as a result of this high pressure compaction procedure was a powder- compacted disc of cohered particles of about 140mm diameter and 20mm in thickness. The disc was machined to provide a billet for high temperature/pressure annealing.
The billet 14 was introduced into the pressure vessel 5 displacing silicone oil which previously filled the vessel 5. The heater was energized and the pressure transducer was allowed to attain a temperature of about 1500C. After 20 minutes the pressure within the vessel was raised to approximately 300 MPa at room temperature. The heaters 12, 13 around both the upper and lower vessels 2, 3 were energized and as the heating proceeded the pressure was allowed to build up until after about 15 minutes a pressure of about 450 MPa was reached.
When a temperature of 230 0 C was reached the pressure was held constant by approximately is withdrawing the piston. Approximately 40 minutes were required to attain this temperature which was within SOC of the required annealing temperature; at this point the temperature was raised at about 0. 50C/minute until the annealing temperature of 2400C was reached, and thereafter these conditions were maintained until the billet was annealed. An annealing time of 0.5 hour at 2400C was generally employed.
After the annealing was completed, heaters of the upper and pressure vessels switched off and an air fan was.employed to cool vessels while the pressure was held constant. initial cooling rate of about SOC/minute employed. After about 20 minutes the vessels cooled to about 1600C and the pressure the were both An was.had was maintained constant during this period. Thereafter the pressure was not controlled but was allowed to drop with decreasing temperature. Even though the pressure was not held constant at this stage, the drop of pressure was such that an undercooling of 800C was observed, but no structural changes occurred. The vessels were allowed to cool further to below 800C before the residual pressure was released and the annealed billet removed from the apparatus. The whole period for this annealing process to provide in the polyethylene the extended chain morphology took between 3 and 4 hours.
HYDROSTATIC EXTRUSION OF THE ANNEALED BILLET Referring to Figure 2, there is shown in cross-section the hydrostatic extruder 1. It employs a Fielding Platt hydrostatic system capable of p I- 11 - is generating up to 7 MPa pressure. The extruder comprises a central barrel 2 which is generally cylindrical and contains a cylindrical pressure chamber 3. One end of the barrel is closed with a plug 4 which is screwed into the end of the barrel. Seated against the plug 4 is the extrusion nozzle 5 which includes a conical portion 6 and which effects the deformation of the billet 7 once the pressure vessel 3 is pressurised such that the billet is urged through the conical section and out to atmosphere to form the extrudate 8. At the opposite end of the barrel to plug 4 there is positioned plug 9 which contains passageways 1.0, the passageways constituting an inlet and outlet for the pressure transmitting fluid, castor oil. The extruder is fitted with electric heaters 11.
In the extrusion procedure, it has been found desirable, because of the brittle nature of the chain-extended linear polyethylene resulting from the annealing process, to employ a brass sheath (not shown) to protect and support the billet during the extrusion process. After loading a machined billet with a matching conical section into the hydrostatic extruder, the chamber 3 was filled with castor oil, and the heaters energized. After about one and a half hours the temperature of the fluid within the chamber 3 had reached 1000C. The pressure transmitted by the castor oil was increased to apply a load to the billet to bring about extrusion. This was achieved with a pressure of 52.5 MPa. When a small portion of the extruded 8 emerged from the -extruder a hauling-off load was applied in order to keep the extrudate in a linear condition. The pressure was then maintained at that value necessary to ensure a constant haul-off speed for the entire is 12 extrusion procedure. The workpiece (or billet) was extruded-through the die at an extrusion speed of up to 2Omm/min.; and speds of about 4mm/min. were usually employed with an imposed deformation ratio of 7. At the termination of the extrusion, the temperature was, in each case, allowed to fall to below 100 0 C before the pressure was released and the extrudate and the remaining end portion of the billet removed from the extruder.
The billet (before extrusion) had an initial melting point of 1420 C and the melting point of the extrudate was 1410 C. 'The Young's modulus of the extruded billet, determined by a three-point bending test at room temperature (10 sec value) was 30.6 GPa. X-ray studies indicated that the polymer of the extruded billet was oriented.
Z1 k
Claims (17)
- CLAIMS i S A process for producing a product comprising linearpolyethylene which process comprises forming a workpiece which is to be extruded in the solid phase by consolidating under heat and pressure a mass of solid particulate linear polyethylene, subjecting the resulting workpiece to heat treatment under pressure to cause the polyethylene to crystallise in an extended chain morphology with the melting point of thepolyethylene being increased to at least 139.50 C and the density to at least 0.98g/cm 3, and thereafter deforming the workpiece of the resulting polyethylene in the solid phase, for example by passage through a die, to provide the polyethylene product whereby the workpiece is subjected to a deformation ratio of at least 3, and preferably 3 to 25.A process as claimed in claim 1 or claim
- 2 wherein the linear polyethylene has a weight average molecular weight (RW) from 300,000 to 37000,000.
- A process as claimed in claim 2 wherein RW is from 350,000 to l.,000,000.
- A process as claimed in any preceding claim wherein the polyethylene is deformed by extrusion to form a bar, strip, rod or tube.
- 5. A process as claimed in any preceding claim wherein the linear polyethylene comprises a 1 1 J 1 i 1 i f iller.
- 6. A process as claimed in any preceding claim wherein the workpiece is extruded under hydrostatic pressure through a reducing die.
- A process as claimed in claim 6 wherein the hydrostatic extrusion is drawassisted hydrostatic extrusion.
- A process as claimed in any preceding claim wherein the ambient pressure at which the deformation is effected is atmospheric pressure.
- A process as claimed in any preceding claim wherein the polyethylene is subjected to a deformation ratio of from 4 to 20.
- 10. A process according to claim 9 wherein the deformation ratio is from 8 to 14.
- 11. A process for imparting extended chain crystalline morphology to linear polyethylene having a weight average molecular weight of at least 300,000, preferably at least 350,000, which process comprises providing the linear polyethylene as solid particulate material, compacting the material by melting only a surface layer of the particles to form a solid, cohered material which is then subjected to a temperature and pressure at which the linear polyethylene crystallises in an extended chain morphology so that the melting point of the polyethylene is increased to at least 139.50 c and the density is increased to at least 3 0.98g/cm - is - is
- 12. A process as claimed in claim 11 wherein the compacted polyethylene is heated to a temperature above 2200C while being maintained in the solid phase by applied pressure.
- 13. A process as claimed in either of claims 11 or 12 wherein the polyethylene is subjected to a pressure of at least 350 MPa during the crystallisation.
- 14. Oriented linear polyethylene having a weight average molecular weight of at least 350,000, and preferably from 350,000 to 1,00,000 which has been deformed to a deformation ratio of from 3 to 20, and which has a Young's modulus of at least 30 GPa and has a melting point of at least 139.50c.
- 15. A process as claimed in claim 1 and substantially as hereinbefore described in the example.
- 16. Polyethylene when produced by the process claimed in any one of claims 1 to 13 or 15.
- 17. A set hydraulic cementitious or organic thermoset mass which incorporates as reinforcement polyethylene according to claim 14 or claim 16.19SE w. -Ine 6C1ri I-E WeR copies be ot:ained-L"or Sales Brancl. St Man. Cray. KentBRE 3RD Printed ky Millupex te,-hr.2q,, ies ltt, S. Ma--T Cray. Kent Con 1 e-
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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GB8717631A GB2207436B (en) | 1987-07-24 | 1987-07-24 | Solid phase deformation process |
US07/379,735 US5096654A (en) | 1987-07-24 | 1989-07-13 | Solid phase deformation process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8717631A GB2207436B (en) | 1987-07-24 | 1987-07-24 | Solid phase deformation process |
Publications (3)
Publication Number | Publication Date |
---|---|
GB8717631D0 GB8717631D0 (en) | 1987-09-03 |
GB2207436A true GB2207436A (en) | 1989-02-01 |
GB2207436B GB2207436B (en) | 1991-07-24 |
Family
ID=10621286
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8717631A Expired - Lifetime GB2207436B (en) | 1987-07-24 | 1987-07-24 | Solid phase deformation process |
Country Status (2)
Country | Link |
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US (1) | US5096654A (en) |
GB (1) | GB2207436B (en) |
Cited By (4)
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GB2235200A (en) * | 1989-07-14 | 1991-02-27 | Nat Res Dev | Polymeric materials |
WO1992011821A1 (en) * | 1991-01-02 | 1992-07-23 | Allied-Signal Inc. | Puncture resistant article |
US5449745A (en) * | 1993-06-01 | 1995-09-12 | Howmedica Inc. | Non-oxidizing polymeric medical implant |
US6800670B2 (en) | 1996-07-09 | 2004-10-05 | Orthopaedic Hospital | Crosslinking of polyethylene for low wear using radiation and thermal treatments |
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IN180653B (en) * | 1992-06-01 | 1998-02-28 | Sree Chitra Tirunal Inst For M | |
CA2166450C (en) * | 1995-01-20 | 2008-03-25 | Ronald Salovey | Chemically crosslinked ultrahigh molecular weight polyethylene for artificial human joints |
US5695698A (en) * | 1996-01-30 | 1997-12-09 | Ajji; Abdellah | Production of oriented plastics by roll-drawing |
US8865788B2 (en) | 1996-02-13 | 2014-10-21 | The General Hospital Corporation | Radiation and melt treated ultra high molecular weight polyethylene prosthetic devices |
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US5814266A (en) * | 1996-05-20 | 1998-09-29 | University Of Kentucky Research Foundation | Method for improving consolidation of powder resin |
FR2753649B1 (en) | 1996-09-26 | 1998-11-27 | PROCESS AND PLANT FOR TREATING PLASTIC TUBES WITH BI-AXIAL DRAWING | |
DE60028370T2 (en) | 1999-04-21 | 2007-05-03 | Howmedica Osteonics Corp. | METHOD FOR THE PRODUCTION OF A SELECTIVELY NETWORKED MEDICAL PROSTHESIS FROM POLYETHYLENE, AND A PROSTHESIS MANUFACTURED THEREOF |
IL149721A0 (en) * | 2000-09-15 | 2002-11-10 | First Quality Fibers Inc | Apparatus for manufacturing optical fiber made of semi-crystalline polymer |
CA2429930C (en) | 2002-06-06 | 2008-10-14 | Howmedica Osteonics Corp. | Sequentially cross-linked polyethylene |
DE10260137B4 (en) * | 2002-12-20 | 2004-11-18 | Schroeter, Johannes, Dr. | Process for the plastic deformation of polymers |
US20050156510A1 (en) * | 2004-01-21 | 2005-07-21 | Chua Janet B.Y. | Device and method for emitting output light using group IIB element selenide-based and group IIA element gallium sulfide-based phosphor materials |
US8262976B2 (en) * | 2004-10-07 | 2012-09-11 | Biomet Manufacturing Corp. | Solid state deformation processing of crosslinked high molecular weight polymeric materials |
US7344672B2 (en) * | 2004-10-07 | 2008-03-18 | Biomet Manufacturing Corp. | Solid state deformation processing of crosslinked high molecular weight polymeric materials |
US7462318B2 (en) * | 2004-10-07 | 2008-12-09 | Biomet Manufacturing Corp. | Crosslinked polymeric material with enhanced strength and process for manufacturing |
IN2009CN02595A (en) * | 2006-11-10 | 2015-08-07 | Dow Global Technologies Inc | |
US8641959B2 (en) * | 2007-07-27 | 2014-02-04 | Biomet Manufacturing, Llc | Antioxidant doping of crosslinked polymers to form non-eluting bearing components |
WO2010096771A2 (en) | 2009-02-20 | 2010-08-26 | The General Hospital Corporation Dba | High temperature melting |
US9586370B2 (en) | 2013-08-15 | 2017-03-07 | Biomet Manufacturing, Llc | Method for making ultra high molecular weight polyethylene |
CA2927056A1 (en) | 2013-10-17 | 2015-04-23 | The General Hospital Corporation | Peroxide cross-linking and high temperature melting |
US11667762B2 (en) | 2017-08-29 | 2023-06-06 | The General Hospital Corporation | UV-initiated reactions in polymeric materials |
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GB2157298A (en) * | 1984-04-13 | 1985-10-23 | Nat Res Dev | Solid phase deformation process |
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GB1480479A (en) * | 1973-06-28 | 1977-07-20 | Nat Res Dev | Process for the production of polymer materials |
DE2634537C3 (en) * | 1976-07-31 | 1980-08-14 | Ruhrchemie Ag, 4200 Oberhausen | Process for the production of molded articles from polyolefins with molecular weights of at least 1 million |
GB2060469B (en) * | 1979-06-06 | 1983-09-28 | Nat Res Dev | Drawing thermoplastics material |
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US4510108A (en) * | 1982-09-29 | 1985-04-09 | The Dow Chemical Company | Method of forming blanks for the solid-phase forming of thermoplastic articles |
US4587163A (en) * | 1984-03-06 | 1986-05-06 | Zachariades Anagnostis E | Preparation of ultra high molecular weight polyethylene morphologies of totally fused particles with superior mechanical performance |
JPS61143113A (en) * | 1984-12-17 | 1986-06-30 | Agency Of Ind Science & Technol | Method for molding low fluidity synthetic resin |
JPS61143112A (en) * | 1984-12-17 | 1986-06-30 | Agency Of Ind Science & Technol | Method for solid phase extrusion of synthetic resin |
JPS61177225A (en) * | 1985-02-04 | 1986-08-08 | Agency Of Ind Science & Technol | Solid state extrusion molding of synthetic resin |
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1987
- 1987-07-24 GB GB8717631A patent/GB2207436B/en not_active Expired - Lifetime
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1989
- 1989-07-13 US US07/379,735 patent/US5096654A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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GB2157298A (en) * | 1984-04-13 | 1985-10-23 | Nat Res Dev | Solid phase deformation process |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2235200A (en) * | 1989-07-14 | 1991-02-27 | Nat Res Dev | Polymeric materials |
GB2235200B (en) * | 1989-07-14 | 1993-02-10 | Nat Res Dev | Polymeric materials |
WO1992011821A1 (en) * | 1991-01-02 | 1992-07-23 | Allied-Signal Inc. | Puncture resistant article |
US5449745A (en) * | 1993-06-01 | 1995-09-12 | Howmedica Inc. | Non-oxidizing polymeric medical implant |
US5650485A (en) * | 1993-06-01 | 1997-07-22 | Howmedica Inc. | Non-oxidizing polymeric medical implant |
US5728748A (en) * | 1993-06-01 | 1998-03-17 | Howmedica Inc. | Non oxidizing polymeric medical implant |
US6372814B1 (en) | 1993-06-01 | 2002-04-16 | Stryker Technologies Corporation | Non-oxidizing polymeric medical implant |
US6664308B2 (en) | 1993-06-01 | 2003-12-16 | Stryker Technologies Corporation | Non-oxidizing polymeric medical implant |
US6818020B2 (en) | 1993-06-01 | 2004-11-16 | Howmedica Osteonics Corp. | Non-oxidizing polymeric medical implant |
US6800670B2 (en) | 1996-07-09 | 2004-10-05 | Orthopaedic Hospital | Crosslinking of polyethylene for low wear using radiation and thermal treatments |
Also Published As
Publication number | Publication date |
---|---|
GB8717631D0 (en) | 1987-09-03 |
GB2207436B (en) | 1991-07-24 |
US5096654A (en) | 1992-03-17 |
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Legal Events
Date | Code | Title | Description |
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732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PE20 | Patent expired after termination of 20 years |
Effective date: 20070723 |