LPPM/ Pt & Pd Certified Reference Materials (CRM) Project Update Hiroshi Sawai International Standardization Section TKG Laboratory Center Tanaka Kikinzoku Kogyo K.K. TANAKA KIKINZOKU KOGYO K.K. 1/19 Our Profile Tanaka Kikinzoku Group is Japanese leading precious metals trader, refiner and manufacturer with a history well over a hundred years. The group is also producer and trader of a variety of materials of bullion and platinum group metals, coins and bars which are acceptable 'good delivery' on most markets and exchanges such as London, New York and Tokyo. The group is also active environmentally, and is one of the world largest recyclers of platinum group metals. 2/19 Session 4 - Sawai 1
Agenda 1.Brief History of LPPM 2. Project Background 3.Importance of CRMs. 4. Project information in general 5. Progress and Plan of LPPM RM Project 6. Material of RM 7. Melting and Casting 8. Ingot of Pt RM1 9. Checking of Ingots using Spark-OES 10. Rolling and Cutting 11. Homogeneity Checking 12. Confirmation by ANOVA 13. Sampling for assaying 14. Future Plan for CRMs 15. Conclusion 3/19 1. Brief History of LPPM In 1973 The London Platinum Quotation was introduced. It was the forerunner of the fixings; a twice-daily indication of the market price for spot platinum, reported by some of the principal companies dealing in the metal. In 1979 The leading London and Zurich dealers reached an agreement to standardise the specifications and provenance of metal which they would accept as good delivery. In 1987 The informal trading which had taken place for many years on a principal to principal basis was formalised via a Deed of Establishment into the London Platinum and Palladium Market. In 1989 The London Platinum and Palladium Quotations were expanded and upgraded to full Fixings. 4/19 Session 4 - Sawai 2
2. Project Background Starting in 2007, the LBMA has produced Au and Ag Certified Reference Materials (CRMs). These first CRMs were useful to validate their existing methods. Metalor, PAMP and Tanaka who are LBMA Referees, had been strongly proposing and advising the importance of CRM of Pt and Pd to the management of LPPM and other LPPM Referees. In 2012, LPPM Management Committee agreed in principle to investigate the viability of producing Pt and Pd CRMs. Late 2013, Tanaka started to make CRMs on behalf of the LPPM. 5/19 5/ 3.Importance of CRMs. 6/ 1. CRMs can be used by the laboratories of refiners and spectrometry instrument manufacturers to validate their existing methods and test materials (used for spectrometer calibration). 2. Each laboratory can use CRMs to validate or assess the assay result of Pt and Pd. 3. By having a set of internationally recognised CRMs, each laboratory will have the ability to compare, and if required, certify their in-house reference materials against CRMs, which will provide the most accurate reference concentration values available. 4. LPPM believes that the use of CRMs by refiners would be beneficial in the current ISO 17025 environment as well. 6/19 Session 4 - Sawai 3
4. Project information in general 1. Steering Committee members LPPM + 5 Good Delivery(GD) Referees 2. Manufactured (both Pt and Pd) by Tanaka Kikinzoku Kogyo K.K. 3. Homogeneity Checking TKK and Metalor 4. Assayed by 5 GD Referees + some more participants. Participants can apply for assay job voluntarily. 5. Adviser on Statistics Dr.Mike Hinds (Royal Canadian Mint) 6. Inquiries in general LPPM or 5 GD Referees 8/19 5. Progress and Plan of LPPM RM Project Process 2013 2014 2015 Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Jan Feb Mar Apr May Jun Jul Procurement of raw materials Refining of Pt Refining of Pd Master alloy making for Pt RM Master alloy making for Pd RM Manufacturing Rolling and Pt-RM 1 Melting 1 Cutting Void Melting 2 Rolling and Cutting Pt-RM 2 Melting OK Rolling and Cutting Pd-RM 1 Melting OK Rolling and Cutting Pd-RM 2 Melting Accept Rolling and Cutting Assay for ingot Pt-RM 1 OK (M-1) OK (M-2) Pt-RM 2 OK Pd-RM 1 OK Pd-RM 2 OK Homogeneity checking Pt-RM 1 Tanaka Metalor Pt-RM 2 Tanaka Metalor Pd-RM 1 tanaka Metalor Pd-RM 2 Tanaka Metalor Judgement Pt-RMs Pd-RM2 PdRM1 Shaving for Assay Assay Shavings distribution Assay by 10 Labs Analysis by Dr. Mike Hinds Completion Products sending to Valcambi 7/19 Session 4 - Sawai 4
6. Material of RM 9/11 Pure Pt Sponge Pure Pt Ingot Master Alloys on Pt matrices 9/19 7. Melting and Casting 10/11 Injection of Master Alloy Melting start Casting 10/19 Session 4 - Sawai 5
8. Ingot of RM LPPM Pt RM 1 Ingot 11/11 Checking sample 11/19 9. Checking of Ingots using Spark-OES LPPM-Pt-RM Ingot assay (mg/kg) Element D.L. RM 1 RM 2 Target Result Target Result Ag 0.3 10 13 50 35 Al 0.7 68 48 As 0.8 50 61 20 32 Au 1.0 10 12 50 52 Bi 0.4 <1.4 20 14 Co 0.3 <1 20 19 Cr 0.3 10 9.4 50 47 Cu 0.5 10 14 100 68 Fe 0.4 10 13 100 91 Ir 3.1 200 200 50 59 Ni 1.8 10 13 50 41 Pb 0.3 20 15 50 31 Pd 0.5 10 10 100 93 Rh 0.7 10 12 100 97 Ru 0.4 10 12 50 49 Sb 3.1 20 20 50 52 Si 0.3 50 27 10 13 Sn 1.2 50 45 10 8.5 Ti 0.3-20 9.4 Tl 0.4 10 6.8 50 30 W 7.9-20 24 Zn 0.3 50 46 10 8.0 Zr 0.3 10 3.7 50 40 LPPM-Pd-RM Ingot assay (mg/kg) Element RM 1 RM 2 Target Result Target Result Ag 10 13.5 100 107.2 Al 20 12.7 5.3 Au 100 96.5 20 17.3 B 10 2.7 0.1 Ca 0.9 20 11.4 Co 10 10.0 20 20.2 Cr 50 52.0 10 10.5 Cu 10 13.1 100 96.0 Fe 10 10.3 50 45.3 Ga 0.1 20 19.2 Ir 10 6.2 50 35.4 Mg 20 23.8 0.3 Mn 20 22.6 0.1 Ni 50 50.5 10 9.8 Pb 10 12.5 50 67.3 Pt 50 44.1 250 203.9 Rh 50 51.9 10 13.3 Ru 10 9.4 50 43.6 Sb 10 8.3 50 40.6 Si 20 54.2 100 140.1 Sn 10 9.3 50 39.5 Zn 10 9.4 20 17.6 Zr 0.2 20 11.0 12/19 12/ Session 4 - Sawai 6
10. Rolling and Cutting 13/ 13/19 11. Homogeneity Checking 14/ Z;1 Z;2 Z;3 Z;4 Z;5 Z;6 Peeling Measure using Spark-OES Z;7 Measuring point Z;8 Z;9 Z;10 Round1 Round2 X:3 X:2 X:1 X:4 Front Side Front Side 14/19 Session 4 - Sawai 7
12. Confirmation by ANOVA 15/ Ex, Cu data on Pt-RM1 Sum of Squares df MS F F crit(0.05) F crit(0.01) Z 0 9 0.04 0.54 2.12 2.89 X 0 3 0.00 0.02 2.84 4.31 ZX 2 27 0.09 1.35 1.77 2.24 SS Error 3 40 0.07 SS Total 5.52 79 Z Average SD 1 25.66 0.21 2 25.76 0.47 3 25.75 0.09 4 25.69 0.12 5 25.61 0.18 6 25.61 0.43 7 25.70 0.26 8 25.83 0.23 9 25.71 0.23 10 25.65 0.27 X Average SD 1 25.71 0.15 2 25.70 0.30 3 25.69 0.28 4 25.70 0.17 By this project, there was no problem on the homogeneity on these RMs except Pd- RM1. Pd-RM1 is confirmed right now.. 15/19 13. Sampling for assaying 16/ Shaving Etching Drying & Sampling 16/19 Session 4 - Sawai 8
14. Future Plan for CRMs Final confirmation & Shaving Until end of March 2015 Shavings distribution April 2015 Assay by 10 labs. Until end of May 2015 Analysis of analytical results by Dr. Mike Hinds Until end of June 2015 Completion : July 2015 17/ 17/19 15. Conclusion 18/ 1. LPPM CRM will be the first ever available international materials of Pt and Pd. 2. Right now, all RMs were made by Tanaka and confirmed of these homogeneity by this project. 3. After finalisation of the certificate, LPPM will supply these CRMs. By having these materials at your plants or assay offices, you will get more confidence on your results by getting a validation of accuracy on your assay method and results. These materials and its procedure will help the PGM market, regulated by LPPM, retain its dignity and reliability. Please join us to change the market toward the right direction and enjoy your business opportunities. 18/19 Session 4 - Sawai 9
Mt.Fuji World Cultural Heritage Thank you for your attention. Please send any inquiries to h-sawai@ml.tanaka.co.jp End/19 21/21 Session 4 - Sawai 10