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Introduction
Theassociationofrubywithtreatmentsthatresultinanadditionofglasstothefinal product began in 1984 with the appearance on the market of Thai origin rubies in which cavities had been filled with glass (Kane, 1984, Scarratt, et al., 1984) a treatmentthathadevolvedintoglasscrackfillingby1987(Hughes,1987,Scarratt, 1987).In1992withthediscoveryofcorundumdepositsintheareaofMongHsu, Burma(Myanmar)thatrequiredhightemperaturefluxheatingregimestobringthe material to market the association of ruby treatments and glass was dramatically expanded(Hlaing,1993,Kremkow,1993,Laughter,1993,Peretti,1993,Smith,etal., 1994). Twenty years after the first association a new rubyglass association a new formofglassfracturefillinginrubyappearedonthemarket(GAAJ,2004,Pardieu, 2005,SmithC.P.,2005,McClure,2006). Pardieu (Pardieu, 2005) noted that some terminology problems may occur about this treatment regarding to the Lead Glass definition as many different formulas canbeused:Pureleadoxide,leadoxidesmixedwithsilicaorfluxeslikeboraxcanbe encountered Temperatures, parameters and result can be very different. Some specificstudieswillprobablybedoneinthefutureregardingtothisissue. Pardieu (Pardieu, 2005) also witnessed the treatment procedure as performed in Chantaburi, Thailand by Master Burner Mahiton Thondisuk and reported that the most suitable rubies for repair are stones with color potential and that are rich in fissures. He stated further that this new treatment is performed currently mostly
on Andilamena rubies (Madagascar) on which Mr. Thondisuk has had extensive experiencebutanyrubymaterialwithfissurescouldberepaired.Itisamultistep treatmentinvolvingsimpleheatingandtheuseofdifferentleadrichcompoundsto fillthefissuresandcavitiesofthestones.Ifmostoftherepairedstonesseenwere largesizestones,stoneslessthan1carathavealsobeentreatedthisway. WhilePardieudidalludetowidetractsofglasscrossingthesurfaceofexampleshe examined in 2004 5 until recently (early 2008) the material observed in laboratories 1 had an equivalence to treatments applied to clarity enhance emeralds (with the use of resins and oils) and diamonds (glass) and therefore the terminologyusedwasadaptedfromthese,i.e.,minor,moderateorsignificantclarity enhancement. In reality the vast majority fell into the significant clarity enhancement category although as McClure (McClure, 2006) points out the efficiencyofthetreatmentissuchthatasinglelargefractureinanotherwiseclean rubycouldbemadetodisappeartotheunaidedeyeexactlyasfilledfracturescan be made to disappear in emeralds and diamonds. In fact, we have already seen several stones that fall into this category. Further and following stability tests laboratories within the Laboratory Manual Harmonization Committee (LMHC) 2 added Glass filler may be unstable to elevated temperatures and to chemical agents.Specialcareshallbetakenwhenrepairingjewelryitemssetwithglassfilled corundum.Duringjewelryrepairtheunmountingofsuchstonesisrecommendedto reportsonthesestones. During a meeting of the LMHC held October 18th 20th 2007 in New York City, Dr. PornsawatWathanakul(ScientificAdvisortotheGITmember)reopeneddiscussions on glass fracture filling in ruby. Several members had noted myriads of large gas bubbleswithinthenewermaterialbeingsubmittedtotheirlaboratoriesandthatin many cases the glass was filling wide seams crossing facets and seemed to be accounting for an ever increasing volume of the finished product. Further, it was surmised from observation that the materialwas being held together by the glass, i.e.theglassactinginsimilarmannertoanadhesive.Followingdiscussionsandan agreementthatthistreatmentwentbeyondwhatmightberegardedasafracture fillingorclarityenhancementprocess,thegroupdecidedtodescribethis(heavily treated)materialasrubyglasscomposites onallfutureidentificationreports. FurtheronNovember13th2007AmericanGemLaboratories(AGL)announcedthat they were changing their reporting policies with regards these stones (AGL, 2007) and indicated that their report wording henceforth would be Identification: CompositeRuby,Standardenhancement:Heat,andAdditionalenhancement:Lead glass.TheyalsoindicatedafurthercommentwouldbeaddedThisrubyhasbeen heavilytreatedusingahighrefractiveindexleadglasstofillfracturesandcavities,
Comparedwiththeprevalenceinthemarketrelativelyfewofthesestoneshavebeensubmittedto laboratoriesforreports. 2 The members of the LMHC are; AGTAGemological Testing Center (USA), CISGEM (Italy), GAAJ Laboratory(Japan),GIAGemTradeLaboratory(USA),GITGemTestingLaboratory(Thailand),Gbelin GemLab(Switzerland),SSEFSwissGemmologicalInstitute(Switzerland)
1
vastly improving the apparent clarity and potentially adding weight. The glass may bedamagedbyavarietyofsolvents. Thispaperdescribesseveralrubiestreatedwithglassandexperimentscarriedout at GIA Laboratory (Bangkok) and at GIA New York that demonstrate the LMHC assumptionthatthestonesarebeingbondedtogetherbyglass.Asanimplication oftheseexperimentsandgiventhatseveralgemstones(ruby,emeraldanddiamond being the most often cited but others including tourmaline and quartz being not uncommon)areclarityenhancedthroughtheinfusionoffractureswithoils,resins and glass, the paper also introduces new (February 2008) nomenclature for describing stones that have been clarity enhanced and those that are clearly composites.
Moreroughwasobtainedastreatedsamplesbutwaslatercutandthesestonesareincludedinthe cutspecimenlist.
The material was examined using Gemolite microscopes in the magnifications rangingfrom10to60xandphotomicrographsrecordeddigitallyusingNikonsystem SMZ1500withaNikonDigitalSightCaptureSystemandavarietyofmagnifications. Fluorescence images were recorded using the DiamondView (The Diamond TradingCompany).ThechemistryoftheglasswasdeterminedwithThermoXSeries II LAICPMS system with an attached New Wave Research UP213 laser. Acid disintegrationtestswerecarriedoutusingconc.50%hydrofluoricacid(HF=20)at roomtemperatureandwithnoorlittleagitation,inanisolatedenvironmentunder anappropriatefumehood.
Inclusion observations
Figure 1 through to Figure 9 shows the typical remaining natural inclusions in the facetedtreatedstones.Silkintheformoffineintersectingneedlesbothinisolated clusters and as part of hexagonal zones were often present as were crystals and negative crystals. None of these inclusions revealed any indications that they had beensubjecttoheating,atleastabove1300C.Thereforeitissurmisedthatanyheat involveinthistreatmentprocessshouldbebelow1300C.ThusconfirmingPardieus observations (Pardieu, 2005) the stones are warmed. In fact, this step is a heat treatment. This step is important to remove the impurities possibly present in the fissures that could create some problems when the glass is added. The heat treatment may also by itself improve the stone color. This warming can be conducted at different temperatures from 900C to 1400C depending on the ruby type.As900Cisnothotenoughtomeltsomeinclusionsasrutile,manystonescan stillhaveanunheatedaspect.Butallstonesareheated. The natural inclusion scenes were largely indicative of some East African and Madagascarsources.
Note:Hydrofluoricacidisdangerousandshouldonlybeusedundercontrolledconditions
Alsoincludedwerecopiousnumbersofbothfattenedandfullyexpanded(Figure10 toFigure16)gasbubbleswithinthetractsofglassineachofthetreatedstones.In many cases the bubbles were so large and/or so prolific that the observers first thoughtsstrayedtowardsaconclusionthatthestonewasalowqualityglassrather thansomethingassociatedwithruby.Thetractsofglassalsowereresponsiblefor the obvious color flashes (Figure 17 to Figure 19) that were visible even to the unaidedeye.Thesecolorflashesbeinginstarkcontrasttosomewhatdifficulttosee colorflashesthathavebeentreatedinthesamemannerbuttoalesserdegree. Inonecasethemicroscoperevealedthattheglassbeingusedhasanorangecolor (Figure20toFigure24).SuchorangecoloredglassisdescribedbyPardieu(Pardieu, 2005)werehestatesInrubiesenhancedinBangkokbyOrangeSapphirecompany, someyellowtoorangecolorconcentrationappearsislargefissuresandincavities. AstatementsupportedbyimagesthatcomparewellwithFigure20toFigure24.He further states The fact that lead glass used in most Chantaburi treatment is pink explainswhyitismostofthetimenotvisibleinsidethegem.
Glassrelatedinclusionsobservedinsomeoftherubyglasscompositesexaminedfor thisreport
Figure10:RGC001flattened bubbleswithinfilledfractures
Figure11:RGC005expanded bubbleswithinfilledfractures
Figure12:RGC006flattened bubbledwithinfilledfractures
Figure13:Flattenedbubbles withinfilledfractures
Figure16:Bubbleswithinfiled fractures
Fluorescenceobservations
In an attempt to further categorize (visually) the volume of glass used in theruby glass composites, 15 of the samples were examined and images recorded with the DiamondView (Diamond Trading Company). These images are produced here fromFigure25toFigure39.Thisexercisewasrewardinginthatitquicklyrecorded images that allowed for a close estimation of the position and volume of glass present in each stone. In particular stones RGC011 and RGC015 revealed copious amountsofglass. DiamondView (Diamond Trading Company) images of specimens RGC001 to RGC015.Glassrevealsitselfaseitherblackorbluetractsrunningacrosseachstone. The brighter red areas reflect the positions of gas bubbles. Sample numbers are givenforeachstone.
Figure25:RGC001
Figure26:RGC002
Figure27:RGC003
Figure28:RGC004
Figure29:RGC005
Figure30:RGC006
Figure31:RGC007
Figure32:RGC008
Figure33:RGC009
Figure34:RGC010
Figure35:RGC011
Figure36:RGC012
Figure37:RGC013
Figure38:RGC014
Figure39:RGC015
Surfacereflectionrelatedobservations
Probablythemostconvenientmethodforlocatingfracturesthatmay(ormaynot) havebeenfilledwithanysubstanceistopositionanoverheadlightandafaceton thesampleinamannerthatachievesneartotalsurfacereflection(NTSF)ofthelight fromthefacetunderexamination.Thestone,beingexaminedonamicroscope,is then turned to achieve NTSF from each facet. In a position of NTSR any inhomogeneity (whether a change in substance, a cavity or a surface reaching fractures)becomesclearlyvisible. Figure 40 to Figure 63 show various facets on the selected 15 test specimens (RGC001RGC015)inNTSF.Allclearlyshowthepresenceglassintractscrossingthe stone(Figure52toFigure57),manyrevealaveritablejigsawpuzzleofrubyandglass (Figure 40 to Figure 51) while others show facets that have an approximate 50/50 rubyglasscomposition(Figure61).
Glasscomposition
The composition of the glass used in the specimens collected for this series of examinationsisindicatedinTable2.
15rubyglasscopositessubjectedtoaciddisintigrationtests(placinginhydrofluoric acidforbetween2and10days)
Figure69:RGC001after aciddisintegration.
Figure73:RGC002after aciddisintegration.
Figure74:RGC003 beforeacid disintegration. Figure76:RGC003 Figure75:RGC003after afteracid aciddisintegration. disintegration. Figure77:RGC003after aciddisintegration.
Figure81:RGC004after aciddisintegration.
Figure85:RGC005after aciddisintegration
Figure92:RGC007after aciddisintegration.
Figure102:RGC010after aciddisintegration.
Figure109:RGC012after aciddisintegration.
Figure113:RGC013after aciddisintegration.
Figure117:RGC014after aciddisintegration
Figure121:RGC015after aciddisintegration.
Discussion
Fromtheaboveobservationsandresultsofaciddisintegrationexperimentsitwould appearthatanadjustmentinreportingnomenclatureisnecessaryandthattheline taken by LMHC (rubyglass composite) is integral with this. However, this single (LMHC)change impacts other reporting areas. These other areas arethose where presently report language describes clarity enhancement (fracture filling) regardless of the stone type and whether this involves glass or some other substance. Themarketcontinuestobewatchedandassessedforanynewdevelopmentstothis orsimilartreatmentprocessesandthisdiscussionpaperwillbeperiodicallyupdated. The following new report nomenclature was introduced for use within GIA LaboratoriesatFebruary1st2008.Suggestionsandfurtherinputiswelcome.
Condition Fissurespresent,butobviouslyintactmaterial
PresumedIntent/ Application
CaseA
Clarity enhancement; SpeciesNatural(Corundum,BerylorTourmalineetc) corundum, emeralds, Variety(Ruby/Sapphire,EmeraldorTourmaline) tourmaline,etc Treatment: Theimagesofrubywithglassheregenerallyreflectthematerialdescribed A (minor, moderate, significant) amount clarity enhancement, using (a filler, inthissectionandwouldalsoreflectthesituationwithemerald. glass,resin,oil)toreducethevisibilityoffissures. Add(indicationsofheating)iffillerisglass. Comment: Fissure filling materials (glass/oil/resin etc) may be unstable to elevated temperatures and to chemical agents. Special care should be taken when cleaningorrepairingjewelryitemssetwithfissurefilledstones
Condition Highly fractured and/or twinned material with filled voids, channels and fissures. Material was one piece initially but may lose integrity if filling material is removed. An exceptionally large amountoffillingmaterialispresent.
CaseB
Species Natural(CorundumorBeryl)with (filler,glass,resin) Variety:(Ruby/SapphireorEmerald)with(filler,glass,oil,resin)
Theimagesofrubywithglassheregenerallyreflectthematerialdescribed Treatment: Fractures filled with (glass/resin) which significantly reduces their inthissectionandwouldalsoreflectthesituationwithemerald. visibility.Add(indicationsofheating)iffillerisglass Comment: Significant fractures present in this stone have been hidden from view by the treatmentdescribedabove.Fracturefillingmaterials(glass/oil/resinetc)maybe unstabletoelevatedtemperaturesandtochemicalagents.Specialcareshould betakenwhencleaningorrepairingjewelryitemssetwithfracturefilledstones
Condition PresumedIntent/ Application 3.Assemblageorbondingofunrelatedgemstone toproducelargecutting pieces(chunksorpowder) material from unusable pieces or powders; currently applies to corundumandberyl Theimagesofrubywithglassheregenerallyreflectthematerialdescribed inthissectionandwouldalsoreflectthesituationwithemerald.
CaseC
Species (CorundumGlass/Berylresin)Composite Variety: (RubyGlass/Emeraldresin)Composite Treatment: Nothingstated Comment: This item is a combination of (ruby / emerald and glass / resin). The binding material may be unstable to elevated temperatures and to chemical agents. Specialcareshouldbetakenwhencleaningorrepairingcompositematerials
Table1
RGC001
Aciddisintegrated
Ct Weight post acid and after drying 0.93 major piece alone including residue 1.00850 major includingresidue piece alone
7.007
5.187
2.782
RGC002
1.29770
6.973
5.613
3.969
RGC003
1.58270
7.920
6.929
3.012
RGC004
1.60520
7.510
5.593
4.245
RGC005
1.83240
8.488
6.381
3.611
RGC006
1.83830
8.390
6.664
3.504
RGC007
2.09230
7.776
6.204
4.919
RGC008
2.47430
8.371
7.279
4.783
RGC009
3.58680
9.491
7.430
5.298
RGC010
5.75550
11.176
9.264
6.267
RGC011
9.84210
14.640
10.280
6.585
Into HF 14:15 November 24th 2007 out 11:00 November 26th 2007. Total 44 hours45mins Into HF 15:22 November 24th 2007 out 10:00 November 26th 2007. Total 44 hours45mins Into HF 16:00 November 24th 2007 out 12:00 November 26th 2007. Total 44 hours45mins th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 out 11:00 th December15 2007.Total107hours
th
1.55 major piece alone including residue 1.58 major piece alone including residue 1.56 major piece alone including residue 1.82 major piece alone including residue 1.67Onlydustleft
2.41 major piece alone including residue 3.11 major piece alone including residue 5.05 major piece alone including residue 8.23 major piece alone including residue 11.19majorpiecealoneincluding residue
Into HF 12:00 December 7 out 11:00 12.72majorpiecealoneincluding th December15 2007.Total107hours residue Into HF 12:00 December 7 2007 out th 11:00 December 15 2007. Total 107 hours th Into HF 12:00 December 7 out 11:00 th December15 2007.Total107hours
th
RGC015
23.86110
16.675
16.437
9.721
Table2
glassonrubycompositeroughsp1 glassonrubycompositeroughsp2 glassonrubycompositeroughsp3 glassonrubycompositeroughsp4 glassonrubycompositeroughsp5 Average Stdev glassonrubycompositeroughsp1 glassonrubycompositeroughsp2 glassonrubycompositeroughsp3 glassonrubycompositeroughsp5 Average Stdev glassonrubycompositeroughsp1 glassonrubycompositeroughsp2 glassonrubycompositeroughsp3 glassonrubycompositeroughsp5 Average Stdev
ppm ppm
7Li 23.61 21.97 21.36 21.78 21.57 22.06 0.90 ppm 59Co 1.30 1.45 1.38 9Be 2.17 2.24 2.08 2.55 2.32 2.27 0.18 ppm 60Ni 29.67 32.55 30.59 30.52 30.09 30.68 1.11 ppm 140Ce 4.85 5.00 5.39 5.76 5.19 5.24 0.36
ppm
11B 17000 15510 15330 15560 15560 15792.00 681.89 ppm 65Cu 8.34 8.92 8.55 8.85 7.89 8.51 0.42 ppm 146Nd 1.96 1.66 2.14 2.35 1.66 1.95 0.30
ppm
24Mg 6933 8177 7815 7583 7103 7522.20 510.17 ppm 66Zn 221.80 231.80 230.60 243.70 246.60 234.90 10.17 ppm 147Sm 0.45 0.38 0.45 0.54 0.34 0.43 0.08
ppm
27Al 198000 180100 198200 214100 185100 195100.00 13266.69 ppm 69Ga 53.61 49.85 52.65 55.65 50.16 52.38 2.43 ppm 153Eu 0.06 0.08 0.10 0.10 0.08 0.08 0.02
ppm
29Si 58510 135600 142100 151900 146500 ######## 38707.49 ppm 71Ga 20.66 21.19 19.59 20.26 20.27 20.39 0.59 ppm 163Dy 0.65 0.55 0.63 0.79 0.54 0.63 0.10
ppm
44Ca 3410 1050 1110 1140 1150 208.00 2022.90 ppm 72Ge 0.87 0.98 0.83 0.86 0.86 0.88 0.06 ppm 172Yb 1.29 1.02 1.27 1.44 1.19 1.24 0.16
ppm
45Sc 13.22 13.52 15.02 16.12 14.41 14.46 1.17 ppm 83Kr 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ppm 175Lu 0.21 0.23 0.26 0.30 0.21 0.24 0.04
ppm
47Ti 1173 1133 1172 1228 1208 1182.80 36.64 ppm 85Rb 6.63 6.21 6.22 6.68 6.30 6.41 0.23 ppm 181Ta 0.43 0.42 0.46 0.49 0.50 0.46 0.04
ppm
48Ti 1173 1135 1163 1219 1198 1177.60 32.32 ppm 88Sr 11.18 9.76 11.40 12.25 10.63 11.04 0.93 ppm 182W 0.20 0.15 0.19 0.25 0.25 0.21 0.04
ppm
51V 15.59 14.91 15.2 15.55 14.75 15.20 0.37 ppm 89Y 5.06 5.08 6.15 6.68 4.99 5.59 0.78 ppm 208Pb 1131000 1042000 1044000 1074000 1090000 1076200.00 36758.67
ppm
52Cr 31.72 52.73 54.66 55.63 55.85 50.12 10.36 ppm 90Zr 1813.00 1772.00 2081.00 2341.00 1777.00 1956.80 250.10 ppm 220Bkg 0 0 0 0 0 0.00 0.00
ppm
53Cr 59.91 55.25 55.45 59.51 56.5 57.32 2.23 ppm 93Nb 1.99 1.97 2.00 2.05 2.05 2.01 0.04 ppm 232Th 1.30 1.32 1.61 1.73 1.39 1.47 0.19
ppm
55Mn 20.24 32.11 29.81 28.59 27.02 27.55 4.49 ppm 118Sn 4.06 3.64 3.54 7.10 4.08 4.48 1.48 ppm 238U 1.76 1.82 1.75 1.85 1.94 1.82 0.08
ppm
56Fe 3188 3098 3155 3289 3217 3189.40 71.10 ppm 137Ba 157.40 150.50 158.40 164.10 154.50 156.98 5.03
glassonrubycompositeroughsp4 1.21
1.26 1.32 0.09 ppm 139La 2.00 2.10 2.39
glassonrubycompositeroughsp4 2.66
2.19 2.27 0.26
References
Kane,R.E.(1984)Naturalrubieswithglassfilledcavities.Gems&Gemology.20.4.187199 Scarratt,K.,etal.(1984)Glassinfillingofcavitiesinnaturalruby.JournalofGemmology.19.4. 293297 Hughes,R.W.(1987)Glassinfillingofcracksinruby.ICALabAlert.4.1 Scarratt,K.(1987)Glassinfillingofcavitiesinrubyandsapphire.JournalofGemmology.20.7/8. 421 Hlaing,U.T.(1993)MongHsurubyupdate.AustralianGemmologist.18.5.157160 Kremkow,C.(1993)Burmaisback:MongHsurubyrushtransformsmarket.ICAGazette.1,9 Laughter,T.(1993)Howdoyoudo?ImfromMongHsu.JewelSiam.4.5.3841 Peretti,A.(1993)ForeignsubstancesinMongHsurubies.JewelSiam.4.5.42 Smith,C.P.,etal.(1994)TheMongHsuruby:AnewtypeofBurmeseruby.JewelSiam.4.6.82 98 GAAJ. (2004) GAAJ Lab Alert: lead glass impreagnated ruby. http://www.gaaj zenhokyo.co.jp/researchroom/kanbetu/2004/gaaj_alert040315en.html Pardieu, V. (2005) Lead Glass Filled/Repaired 04.http://www.aigslaboratory.com/Filearticle/55.pdf Rubies, Version
Smith C.P., M. S. F., Wang W., Hall M. (2005) Some characteristics of leadglassfilled corundum.JewelleryNewsAsia.November.255.7984. McClure, S. F., Smith, C.P., Wang, W., Hall, M. (2006) Identification and Durabuility of Lead GlassFilledRubies.Gems&Gemology.42.1.2234 AGL. (2007) AGL Modifies its Disclosure Policy Rubieshttp://www.aglgemlab.com/AGLModifiesDisclosure.html on LeadGlass Filled
Composite materials (or composites for short) are engineered materials made from two or
more constituent materials with significantly different physical or chemical properties and which remain separate and distinct on a macroscopic level within the finished structure. http://en.wikipedia.org/wiki/Composite_material