The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC
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    The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    This forum is littered with threads on the subject, but they usually are not very enlightening. Attempts have been made at an overview, but that hasn't stopped the question from reappearing. Hopefully this thread will change all that!

    In this first post I will list interesting previous discussions and notable quotes. Later on I will adress some common misconceptions (like scratch resistance does not equal scratch proof) and discuss the past and present of Citizen titanium.

    From: https://forums.watchuseek.com/f9/dura...lc-303581.html
    Quote Originally Posted by RPF View Post
    The big three Japanese watchmakers have been quietly adding scratch-resistant watch cases and bracelets to their lineup since the 90s, especially Citizen.

    To date, very few of these watches have been offered to the international market, which explains the dearth of English literature on these technologies.

    I'd like to offer a brief walk-through of the various terms one will come across shopping for a high-end JDM quartz.

    First, trademarks.

    Duratect is a marketing term registered by Citizen. It is Japlish for dura-techko or durable technology. A Duratect marked watch (on the caseback) has been surface treated, but a variety of methods are used on different models to achieve different levels of hardness and finish. In short, it is not descriptive to say Duratect. Rather the type of Duratect, for example, TIN, TIC, PTIC, MRK, DLC, GTIC, IP or combinations thereof must be specified.

    [This is analogous to saying "that is a Citizen". No material information is communicated because Citizen has too many model lines to begin with.]

    Brightz and Diashield are registered by Seiko. Brightz is a Seiko developed Ti alloy that's 30% harder than steel, and much harder than regular Ti. The main advantage though, is it's virtually indistinguishable from SS. A Brightz watch scratches about as easily as an SS one, but is much lighter.

    Diashield is Seiko's version of DLC, and many new JDM models are Diashield treated. These include SS, Ti and Brightz models. Unfortunately, it appears the Diashield quality correlates with price band. The performance and aesthetics of a Diashield Spirit lags behind a Brightz, for example. It's possible the softer Ti on the Spirit is to blame though.

    DLC, CVD (TIC/TIN and similar), IP etc refer to the hardening technologies, as they are commonly known. Casio employs all these methods in their Oceanus and MRG lines, which are Ti only. The only difference between Casio and their competitors is the absence of branding such as Duratect (a rather confusing term) and Diashield.

    Next time the question "Which is better, Duratec or bright?" comes up, just note that 1) the spelling is way off and 2) the answer is way more involved than a yes-no.

    I hope this short vocab guide makes it easier for the confused.

    I'll take a stab at the how-to in metals hardening if there is interest.
    From: https://forums.watchuseek.com/f21/sei...ec-253509.html
    Quote Originally Posted by El @ View Post
    Since this has been resurrected and is walking, check what Seiya Kobayashi has to say on the matter. Scratch-resistant "Dia-Shiled" "Duratect" "DLC"...... €“ seiyajapan.com

    I often get asked just how tough (the case and bracelet) the metal Dia-Schild and Duratec (scratch-resistant) metal truly is.
    I created a chart for easy reference.
    They are lined up in order of toughness according to Hv (Vickers Hardness) ranking system.
    They get tougher the further you go to the right.
    "DiaShield" is about 2-3 times harder than Stainless Steel.
    "Duratect/DLC" is about 5-7 times harder.
    "Duratect α" is about 10 times harder. It is the same as Sapphire crystal.

    It is used in models such as the AT9050-58A "Citizen Exceed".
    There is this much of a difference between Seiko and Citizen.(SEIKO may currently be developing new technology.)
    The DLC(Diamond-like Carbon) doesn't mean that is is just as hard as a diamond、but that it has a structure similar to a diamond.
    As a final note, even though they are tough to scratch, it doesn't mean that they can't be.

    Also interesting, though full of erroneous views: https://forums.watchuseek.com/f21/dif...2e-634725.html

    Some user experience: https://forums.watchuseek.com/f9/trut...ce-181216.html

    All details about the different Citizen surface treatments can be found in later posts.
    Last edited by CitizenPromaster; September 9th, 2016 at 12:28.

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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    OK, MISCONCEPTION 1. Titanium that is treated will not scratch easily, or untreated titanium scratches easier than stainless steel.

    First of all, titanium, no matter the treatment, WILL scratch and ding. My 8 year old Promaster Pilot Chrono is full of both scratches and dings. However, compared to my 'simple' old Lorus (gray) titanium chronograph, the Ti +IP does look considerably better (from a distance). Be warned though, many people have been very disappointed or put off by how easy or visibly titanium scratches. Some say basic titanium has self-healing properties because a new TiO2 oxidation layer is grown, but it doesn't perform wonders.

    Example:
    Quote Originally Posted by J.D.B. View Post
    I have a C-650 Skyhawk and it's got plenty of scratches in the fine blasted surface. Yup there ARE several grades of Ti out there.
    Josh
    This poll gives a pretty solid verdict as well: https://forums.watchuseek.com/f2/does...ss-199231.html

    As I said before, Duratect has the best reviews, and DLC (Diamond Like Carbon) as well. https://forums.watchuseek.com/f17/jus...ce-166223.html

    The best Duratect out there is Duratect Alpha, but that is applied to only the most expensive models. None-Alpha modern JDM Duratect (as marked on caseback) seems to work great too though*. So if you are not into babying your watch, it might serve you well to pay extra for a JDM version with Duratect marking on the caseback. Downside is that finding them might be hard and until recently the JDM radio controlled watches usually only sync in Japan. These days the RC limitation is less of an issue because of multiband calibers.

    *Please note: the stronger and darker JDM Duratect that many WUS users have experienced is AFAIK only part of the JDM Promaster line, as explained in the next post.
    Last edited by CitizenPromaster; August 18th, 2016 at 12:23.
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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    MISCONCEPTION 2: Ti + IP and Duratect are a coating and when you scratch it you are done, it's impossible to refinish.

    Well you can debate the terminology, as in the bottom quote in this post, but in any case it is not a 'painted' or spray applied coating but a surface treatment. The process differs for Ion Plating (IP), DLC (cold plasma) and MRK (curing) and so does the (depth of) the result.

    For all intents and purposes, in EU/USA the term Super Titanium = Ti + IP = basic Duratect, though an EU/USA watch will not say Duratect on the caseback. However, the JDM Duratect we see on a Promaster JDM is slightly darker in color and reportedly more scratch resistant. And to add to the confusion, in Japan they use Super Titanium as a blanket term for all variations of Duratect.

    My interpretation is that the EU marketing term 'Super Titanium' is Duratect TIC (see below images and Japanese table), equal in hardness to the EU marketing term Ti + IP = Hv1000-1200.

    After my research for this thread I'm pretty certain the stronger and slightly darker Duratect we experience specifically on grey import JDM Promaster watches, where it says Duratect on the caseback, is in fact Duratect MRK = Hv1300-1500. MRK is AFAIK never mentioned on the watch/caseback. According to the below info it is used only on the (JDM) Promaster watches, which corresponds with WUS user experience as mentioned before.

    DLC is easily recognised because it makes the watch appear black depending on the light. AFAIK there is never mention of DLC on the watch itself.








    The images above seem to suggest Titanium Nitride (TIN) is involved in the process, but Citizen Japan only ever mentions Titanium Carbide (TIC) as the resultant coating. See below.

    From the Japanese site with google translate, Original: http://citizen.jp/technology/detail/duratect
    The alignment is a bit off here, everything up to DLC is Ion Plating technology.

    Dyuratekuto
    それは、やわらかな発想から生まれた『硬い』技術です。
    It is born from the soft idea "hard" technology.



    デュラテクトとは、時計のケースやバンドに特殊な加工処理をすることで、日常使用によるすり傷や小傷から、 時計本来の輝きや仕上げの美しさを保護するためにシチズンが独自に開発した表面硬化技術の総称 です。
    The Dyuratekuto, by a special processing to watch cases and bands, from scratches and small scratches due to everyday use, Citizen in order to protect the beauty of the original shine and finish clock's proprietary surface is the generic name of curing technology.

    加工技術
    Processing technology
    名称
    name
    主な特長
    Key Features
    ピッカース硬度
    Pikkasu hardness
    IP技術
    IP technology
    デュラテクトα
    Dyuratekuto α
    シチズン独自の表面硬化技術【Duratect】に、最高峰となる新技術「デュラテクトα」が 登場します。
    Citizen on its own surface hardening technology [Duratect], new technology that becomes the highest peak "Dyuratekuto α" will appear.
    従来のデュラテクトTIC/PTICより2倍以上の硬さを実現しました。
    It has achieved a conventional Dyuratekuto TIC / 2 times more hardness than PTIC.
    貴金属を含まない素材をコーティングすることで、キズに強いだけでなく肌にも優しいのが特徴で す。
    By coating a material that does not contain precious metals, the gentle to the skin as well as a strong scratch is characterized.
    カラーラインナップもWhite(SD-W)、Metal Gray(SD-MG)、Rose(SD-R)の3色が可能。
    Color lineup White (SD-W), Metal Gray (SD-MG), can be three colors of the Rose (SD-R).
    貴金属に劣らない高級品に相応しい輝きも備えています。
    Shine worthy of the luxury goods that is not inferior to the precious metal also provides.
    Hv2,000~2,500
    Hv2,000 ~ 2,500
    デュラテクトTIC
    Dyuratekuto TIC
    IP技術を用いて硬化被膜をコーティングし、表面を硬質化。
    Coated with a cured film using the IP technology, harden the surface.
    鏡面仕上げおよびヘアーライン仕上げが可能となります。
    Mirror finish and brushed will be possible.
    ・チタニウム色調を生かし、主にチタニウム商品に採用。
    - Taking advantage of the titanium color, mainly employed in titanium products.
    Hv1,000~1,200
    Hv1,000 ~ 1,200
    デュラテクトPTIC
    Dyuratekuto PTIC
    デュラテクトTICに貴金属であるプラチナをさらにコーティング。
    Further coated with platinum is a precious metal to Dyuratekuto TIC.
    硬度の高いまま、その厚みを制御することで、プラチナの美しい色調やステンレスと同等の色調を 実現。
    Remains high hardness, by controlling the thickness, realizing a beautiful color or stainless steel equivalent to the color tone of the platinum.
    ・主に高級品、女性用商品に採用。
    Mainly luxury goods, adopted in women's products.
    Hv1,000~1,200
    Hv1,000 ~ 1,200
    デュラテクトGOLD
    Dyuratekuto GOLD
    独自のIP技術を用いて、窒化チタン皮膜上に金と合金化合物をコーティング。
    Using its own IP technology, coated with gold and alloy compound on the titanium nitride film.
    従来不可能とされていた金色デュラテクトを実現しました。
    It has achieved a gold Dyuratekuto which has been considered to be conventional impossible.
    Hv1,300~1,500
    Hv1,300 ~ 1,500
    デュラテクトPINKGOLD
    Dyuratekuto PINKGOLD
    デュラテクトGOLD同様に、窒化チタン被膜上に金と合金化合物をコーティング。
    Dyuratekuto GOLD Similarly, coating the gold and alloy compound on the titanium nitride coating.
    華やかなピンクゴールドを実現しました。
    It was realized a gorgeous pink gold.
    Hv1,200~1,400
    Hv1,200 ~ 1,400
    低温プラズマ技術
    Low-temperature plasma technology
    デュラテクトDLC
    Dyuratekuto DLC
    DLCとはDiamond Like Carbonの略で、主に炭素と水素で構成される非品質のカーボン硬質膜をコーティング。
    A substantially, mainly coating the non-quality carbon hard film composed of carbon and hydrogen of Diamond Like Carbon is the DLC.
    精悍なダークグレー色でデュラテクトのバリエーションが拡大。
    Expansion variations of Dyuratekuto in fearless dark gray color.
    Hv1,000~1,400
    Hv1,000 ~ 1,400
    デュラテクトDLC/MRK
    Dyuratekuto DLC / MRK
    ガス硬化技術により、表面を硬質化したチタン素材にDLCをコーティング。
    By gas curing technology, coating the DLC the surface to harden the titanium material.
    Hv1,000~1,400
    Hv1,000 ~ 1,400
    ガス硬化技術
    Gas curing technology
    デュラテクトMRK
    Dyuratekuto MRK
    チタン素材に、窒素と酸素を表面から浸透させて、素材の表面を硬化処理しました。
    The titanium material, the nitrogen and oxygen to penetrate from the surface, has been curing process the surface of the material.
    キズがつきにくい、鏡面処理を実現しました。
    Scratch-resistant, it has realized the mirror surface processing.
    ・過酷な環境で使われるスポーツウオッチに採用。
    And adopted in sports watches to be used in harsh environments.
    Hv1,300~1,500
    Hv1,300 ~ 1,500
    「DURA(デュラ)」はラテン語で”硬い”の意味。
    The meaning of "DURA (Dura)" is a Latin word "hard".
    Hvビッカース硬度:Vickers Hardness 材料の硬さを表す尺度。
    Hv Vickers hardness: measure of the hardness of Vickers Hardness material.

    表面硬化技術
    Surface hardening technique



    IP技術(PTIC(プラチナチタンカーバイト)/TIC(チタンカーバイト)/GOLD(ゴール ド))
    IP technology (PTIC (platinum titanium carbide) / TIC (titanium carbide) / GOLD (Gold))




    IP(イオンプレーティング)とは真空装置の中で金属をイオン化し部品の表面に被膜をコーティングする技術 です。
    IP is the (ion plating) is a technology for coating a coating on the surface of the ionized part of the metal in a vacuum device.
    乾式めっきとも呼ばれ、腕時計には主に装飾目的で使用されてきました。
    Also referred to as dry plating, has been used mainly for decorative purposes is to watch.
    シチズンでは独自の技術により硬質被膜のコーティング処理に成功。
    Citizen success in the coating process of the hard coating by unique technology.
    部品の材質、形状、仕上げにとらわれず適用範囲が広く、カラーバリエーションも豊富です。
    The material of the parts, shape, wide range of application agnostic to finish, color variation is also abundant.
    高級品、レディス、チタン商品と幅広いモデルに展開されています。
    Luxury goods, ladies', has been deployed in titanium products and a wide range of models.


    低温プラズマ技術(DLC(ダイヤモンドライクカーボン))
    Low-temperature plasma technology (DLC (diamond-like carbon))



    プラズマCVD技術とは真空装置の中で原料物質を含むガスをプラズマ化し、化学反応させたのちに部品の表面 に吸着コーティングする技術です。
    Plasma The CVD technology into plasma gas that contains the raw material in a vacuum device, is a technology that adsorption coating to the surface of the component in the mixture was allowed to chemical reaction.
    DLC被膜はダイヤモンド構造を一部含んだC(炭素)とH(水素)からなるアモルファス構造をとり、結晶粒 界がないため高硬度で非常に滑らかな被膜です。
    DLC coating takes an amorphous structure consisting of containing a part of the diamond structure C (carbon) and H (hydrogen), is very smooth coated with a high hardness because there is no crystal grain boundaries.
    独特なダークグレー色は高級品、ファッションモデルのバリエーションのひとつとして拡大展開中 です。
    Unique dark gray color luxury goods, is expanding deployment as one of the variations of the fashion model.



    ガス硬化技術(MRK)
    Gas curing technology (MRK)



    真空炉に窒素と酸素を封入し、熱処理を施すことでチタン素材の表面に20~30μmの硬化層を形成させるこ とにより時計の表面を硬質化する技術です。
    Nitrogen and oxygen enclosed in a vacuum oven, is a technique for hardening the surface of the watch by forming a cured layer of 20 ~ 30 .mu.m on the surface of the titanium material by heat treatment.
    『軽い・錆びない・金属アレルギーを起こしにくい』というチタンの特性はそのままでケース表面の硬質化に成 功しました。
    Characteristics of titanium called "less prone to light not rust-metal allergy" has succeeded in hardening of the surface of the case as it is.
    ハードな使用環境下で効果を発揮し、チタンのスポーツモデルに採用されています。
    To demonstrate the effect under hard use environment, it has been adopted in titanium sports model.


    複合硬質化技術(DLC/MRK)
    Composite hard technology (DLC / MRK)




    ガス硬化技術の「MRK」と低温プラズマ技術の「DLC」の特徴を兼ね備えた表面改質技術で、チタンのスポ ーツモデルに拡大展開されています。
    Features a combines surface modification techniques of "DLC" in the low-temperature plasma technology with the "MRK" of gas curing technology, it has been expanded deployment to titanium sports model.


    傷つきにくさの比較
    Comparison of the wounded difficulty



    当社耐傷試験機によるデュラテクト加工前と加工後の耐擦傷効果の比較
    Comparison of scratch effect after processing and before Dyuratekuto processing by the Company scratch testing machine

    試験条件:SiO2粉末混合天然ゴムにて2kg荷重・30回スライド磨耗(当社規格)
    Test conditions: SiO2 powder mixed with natural rubber 2kg load, 30 times slide wear (our standard)
    ※注意:硬いものに擦りつけたり、強い衝撃を加えると傷や打痕がつく場合がありますのでご注意く ださい。
    ※ Note: or rubbed on the hard thing, please note that you may get is the addition of a strong shock scratches and dents.
    表面硬化処理ですので、素材そのものの硬化ではありません。
    Since it is a surface hardening treatment, not a cure of the material itself.

    材質硬度について
    About Material hardness



    代表的なケース(側)材質のビッカース硬度
    A typical case (side) Material of Vickers hardness

    ビッカース硬度(Hv)
    Vickers hardness (Hv)
    ビッカース硬度は、素材にダイヤモンド製の圧子を押し込むことで測定されます。
    Vickers hardness is measured by pushing the diamond of the indenter to the material.
    この試験方法は、極めて硬い材料も測定でき、また試験用途も大変広く、他の硬さ試験の基準にも利用されてい ます。
    This test method is also extremely hard material can be measured, also testing applications also very widely, has also been used on the standard of the other hardness test.
    表面被膜硬度については、低荷重で被膜硬度のみを測定したものです。
    For surface coating hardness, it is a measure of the only film hardness at low load.
    日常使用による傷のつきにくさをそのまま表現する尺度ではありません。
    It is not a measure to directly express the luck difficulty of scratch due to everyday use.

    耐摩耗性と美しい黒を実現するデュラテクトDLC
    Dyuratekuto DLC to achieve a beautiful black and wear resistance




    DLCとはDiamond Like Carbon(ダイヤモンドのようなカーボン)の略で、主に炭素と水素で構成される非晶質のカーボン硬質膜 のことです。
    The DLC stands for Diamond Like Carbon (carbon, such as diamond), is mainly that of amorphous carbon hard film composed of carbon and hydrogen.
    素材によって応用範囲が限定されていた表面加工技術DLCを独自の技術で改善。
    Improve the surface processing technology DLC the range of applications has been limited by the material in its own technology.
    従来難しかった素材への加工が可能となり、シチズン独自の<デュラテクトDLC>が高い耐摩耗性を持つ硬く 美しい黒のケースやバンドを実現します。
    It enables processing of the conventional was difficult material, providing a beautiful black case and band hard with the Citizen own <Dyuratekuto DLC> a high wear resistance.



    More WUS discussion on technology.

    Quote Originally Posted by RPF View Post
    A short discussion on the above, leaving out the specifics.

    1. Hard materials: This is the most straightforward solution employed by Rado, predominantly ceramics and hardmetal. Hardmetal offerings from Chinese case suppliers are also on the rise.

    Material strength and fracture toughness is in general, inversely proportional to hardness. Harder materials are more difficult to work with, due in part to the brittle nature.

    Unlike SS or other metals shaped by CNC out of case blanks, ceramic/hardmetal cass are sintered from powder fed at high pressure into precision moulds. It is difficult to control tolerances due to machining difficulties post-forming. This affects the water resistance and is one reason (I believe) we have not seen a hardmetal dive watch. Screw backs are also troublesome for ceramics due to torque load.

    Note: Sintering is just a fancy way of saying baking.

    Overall, hardmetal is comparable in hardness to ceramics but has greater mechanical and fracture toughness. However, it is also much heavier, with a density approaching that of gold (SG 14-17, depending on binder used).

    The main disadvantages of these materials are cost, brittleness, finishing difficulties and the high-tech, non-metal look on what is essentially, jewelry.

    Note: Brightz is mentioned because this alloy retains the weight and strength attributes of Ti while improving aesthetics and hardness.

    2. Hard coatings: Most people are familiar with this, associating PVD with black metal watches.

    We can add ion plating, ceramic coatings (rare) and DLC to the mix. Performance varies depending on substrate and thickness but the mechanical strength of the base material (SS, Ti etc) is not compromised. Coatings also improve corrosion resistance, although that's almost never a selling point on watches. (That is one reason why I never understood the use of 904 in watches.)

    Application is similar to spray painting in a specialized chamber.

    The main disadvantages are limited finishing options and poor ding (unless in tandem with other technologies) and scratch (DLC is an exception) resistance. Scratches that expose bare metal ruin the aesthetics more than on a plain metal watch.

    3. Hardened matrix: Standard machining workflow can be employed on traditional materials before the metal is hardened via heat or surface treatment. The finished product has the benefit of precise tolerances, superior wear characteristics and similar aesthetics to the original alloy.

    Metals can be hardened two ways, throughout the matrix or just the surface, producing a functionally graded material.

    Damasko heat treats their ice-hardened steel to a uniform >60 HrV, similar in hardness to other martensitic steels such as S30V used on premium knives. Quite impressive given the complexity of a watch case compared to a blade.

    Better scratch resistance can be achieved through surface treatment, usually by diffusing carbon and nitrogen into the matrix. The hardness decreases with the penetration of the atoms, producing a material that's hard on the outside and tough on the inside.

    Sinn's Tegiment and various versions of Citizen's Duratect employ this method. I've been told IWC also treats several of their Ti models in similar fashion but I've not explored this further.

    One argument against surface treatment is the eggshell effect. The surface may resist scratches, but risks deformation due to the underlying soft metal. This is a valid concern but it should be highlighted an untreated watch will deform to a greater degree.

    Surface treated metals usually appear dull and cannot be refinished by hand.

    ***

    Personally, I consider combinations of 2&3 to be the best compromise in terms of machining, scratch and ding resistance. Currently, Casio, Citizen, Seiko and a couple of Swiss brands have introduced models which are surface hardened, IP coated and DLC-ed. These are probably the best cases around, even though the ceramic/lanthanum/diamond cases of Rado are harder. For one, they have better tolerances, are lighter and mechanically stronger.
    Last edited by CitizenPromaster; August 19th, 2016 at 13:07.

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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    Studying the above post carefully should answer pretty much all questions about Citizen's titanium treatments, except for: can you refinish Duratect and/or Super Titanium?

    Well the jury is still out on this one. Basic Ti that is brushed for sure cleans up nicely and easily with the right material like Scotchbrite. There are a few examples on WUS, here is one: https://forums.watchuseek.com/f2/scra...s-3154634.html and another: https://forums.watchuseek.com/f71/let...l#post24317242 I'm not sure about blasted/satin though.

    The below bracelet of a Citizen Chronomaster is supposed to be Duratect, but on stainess steel and it will both scratch AND refinish!

    Quote Originally Posted by rex View Post
    This is what it looked like after approximately 2 years of wear. Not very impressive, IMO.



    So I sent the watch back to Japan for a make-over and she came back like this. I bet all they did was polish out the scratches and did not re-apply the Duratech coating.

    My solution has been buying a second original titanium bracelet for my Pilot Chrono (expensive solution btw) so I can fully refresh down the road if I want to, but mostly to even be able to replace a broken bracelet after decades!
    Last edited by CitizenPromaster; September 2nd, 2016 at 19:34.
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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    In my final post for today, I want to follow up the clarification with some new confusion, because all of the above applies to modern Citizens, probably post 2005. Citizen has a long relationship with titanium and surface treatment and has improved it over the years. I dug up an old Citizen website from 2001 that explains (in Japanese) what Titanium they use. Duratect didn't even exist yet, the best they had was Dura Titan at Hv600-800.

    So if you have an older (90s, early 2000s) titanium Citizen all bets are off. This brings us to MISCONCEPTION 3: underneath the fancy coating Citizen uses cheap a$$ (Grade 2 or whatever) titanium.



    Now I am not saying Citizen uses Grade 5 (Ti6Al4V), I think they don't, but the first row in the below 'yellow' table seems to suggest Citizen doesn't use 99,7% titanium, which is 'pure' titanium like Grade 2. However, you might also say that all that is claimed in the first row is that Citizen doesn't use 99,7% grade titanium at the surface. What they actually use is anyone's guess, there are 38 grades! https://en.wikipedia.org/wiki/Titanium_alloy So I don't feel confident to say the misconception is truly a misconception, but it is likely Citizen has their own alloy recipe by now.

    All I know is that the world's first watch with titanium case, the 1970 Citizen X8 Chronometer is often described as being 99,6% titanium. One was even for sale on WUS: https://forums.watchuseek.com/f29/fs-...er-863955.html And here's another nice review: https://sweep-hand.org/2013/12/22/th...m-chronometer/

    In this official Citizen picture the X8 is pretty dark grey, as you would expect for pure titanium, but the sweep-hand example I find surprisingly light in tone. That could be 40 years of growing a titanium dioxide (TiO2) skin though.





    So here's what Citizen says in 2001 (via Google translate).

    Last edited by CitizenPromaster; August 19th, 2016 at 18:34.
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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    This video on Citizen Super Titanium is not very informative, but it contains some nice imagery.
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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    Let me give you an example of a Promaster watch in non-JDM and JDM spec.

    Here is the JDM CB0130-51E, notice the laser engraved Duratect on the caseback. For some reason Citizen also only provides the micro-adjustable clasp to JDM models




    And here is the non-JDM (Asia?) CB0131-59E. The dial says Eco-Drive, and you can see Duratect is missing from the caseback, though it still says titanium in small print.




    It's hard to see any color diference in this comparison.

    Personal note: if I didn't have my AS4050-51E, I would try to source a JDM CB0130-51E, it even receives EU and USA! I like the bracelet I have better though.

    Speaking of my watch, it's the EU version (marketed as Ti+IP) of the JDM PMP56-2931, which in turn is the more affordable version of the JDM PMP56-2933 from 2006. The 33 was the first Citizen in Duratect MRK + Duratect DLC, which made it very expensive. Only Japanese RC reception though. Now the color difference is very obvious due to DLC. Color diference between AS4050-51E and PM56-2931 could be due to lighting.

    A4050-51E



    PMP56-2931


    PMP56-2933



    Notice again Duratect on caseback and micro-adjustable clasp.





    If you haven't realised yet, the PMP is pretty much my grail watch, here is some user experience on wear and tear: https://forums.watchuseek.com/f21/ult...ct-679839.html
    Last edited by CitizenPromaster; September 1st, 2016 at 18:37.

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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    Coincidentally, while making and updating this thread, Citizen Japan has updated it's Duratect page. The URL changed and they changed the scratch test info. In the one above they showed how MRK is superior to TIC. In the new one the superiority of Duratect Alpha is shown. New link: ƒ‡ƒƒƒ†‚ƒˆ [CITIZEN-‚ƒ‚ƒ…•™‚ˆ] Translation below.

    It is born from the soft idea "hard" technology.
    デュラテクトとは、時計のケースやバンドに特殊な加工処理をすることで、日常使用によるすり傷や小傷から、 時計本来の輝きや仕上げの美しさを保護するためにシチズンが独自に開発した表面硬化技術の総称 です。
    The Dyuratekuto, by a special processing to watch cases and bands, from scratches and small scratches due to everyday use, Citizen in order to protect the beauty of the original shine and finish clock's proprietary surface is the generic name of curing technology.
    加工技術
    Processing technology
    名称
    name
    主な特長
    Key Features
    ピッカース硬度
    Pikkasu hardness
    IP技術
    IP technology
    デュラテクトα
    Dyuratekuto α
    従来のデュラテクトTiC/PTiCより2倍以上の硬さを実現しました。
    It has achieved a hardness of more than twice than that of the conventional Dyuratekuto TiC / PTiC.
    キズに強いだけでなく高級品に相応しい輝きも備えています。
    Shine worthy of the luxury goods not only strong in the scratch also equipped.
    White(SD-W)、Metal Gray(SD-MG)、Rose(SD-R)の3色が可能。
    White (SD-W), Metal Gray (SD-MG), can be three colors of the Rose (SD-R).
    Hv2,000〜2,500
    Hv2,000~2,500
    デュラテクトTIC
    Dyuratekuto TIC
    IP技術を用いて硬化被膜をコーティングし、表面を硬質化。
    Coated with a cured film using the IP technology, harden the surface.
    鏡面仕上げおよびヘアーライン仕上げが可能となります。
    Mirror finish and brushed will be possible.
    ・チタニウム色調を生かし、主にチタン商品に採用。
    - Taking advantage of the titanium color, mainly employed in titanium products.
    Hv1,000〜1,200
    Hv1,000~1,200
    デュラテクトPTIC
    Dyuratekuto PTIC
    デュラテクトTICに貴金属であるプラチナをさらにコーティング。
    Further coated with platinum is a precious metal to Dyuratekuto TIC.
    硬度の高いまま、その厚みを制御することで、プラチナの美しい色調やステンレスと同等の色調を 実現。
    Remains high hardness, by controlling the thickness, realizing a beautiful color or stainless steel equivalent to the color tone of the platinum.
    ・主に高級品・女性用商品に採用。
    Mainly used in luxury goods and women for the commodity.
    Hv1,000〜1,200
    Hv1,000~1,200
    デュラテクトGOLD
    Dyuratekuto GOLD
    独自の加工技術を用いて、硬質皮膜上に金と合金化合物をコーティング。
    Using a proprietary processing technology, coated with gold and alloy compound on a hard film.
    従来不可能とされていた金色デュラテクトを実現しました。
    It has achieved a gold Dyuratekuto which has been considered to be conventional impossible.
    Hv1,300〜1,500
    Hv1,300~1,500
    低温プラズマ技術
    Low-temperature plasma technology
    デュラテクトDLC
    Dyuratekuto DLC
    DLCとはDiamond Like Carbonの略で、主に炭素と水素で構成される非晶質のカーボン硬質膜をコーティング。
    A substantially, mainly coating the amorphous carbon hard film composed of carbon and hydrogen of Diamond Like Carbon is the DLC.
    精悍なダークグレー色でデュラテクトのバリエーションが拡大。
    Expansion variations of Dyuratekuto in fearless dark gray color.
    Hv1,000〜1,400
    Hv1,000~1,400
    ガス硬化技術
    Gas curing technology
    デュラテクトMRK
    Dyuratekuto MRK
    チタン素材にガスを表面から浸透させて素材の表面を硬化処理しました。
    Titanium material by penetration of gas from the surface has hardened the surface of the material.
    キズがつきにくい、鏡面処理を実現しました。
    Scratch-resistant, it has realized the mirror surface processing.
    ・過酷な環境で使われるスポーツウオッチに採用。
    And adopted in sports watches to be used in harsh environments.
    Hv1,300〜1,500
    Hv1,300~1,500
    複合硬化技術
    Composite curing technology
    デュラテクトDLC/MRK
    Dyuratekuto DLC / MRK
    ガス硬化技術により表面を硬質化したチタン素材にDLCをコーティング。
    Coating the DLC the surface by gas curing technology in hardening the titanium material.
    Hv1,000〜1,400
    Hv1,000~1,400
    デュラテクトα/MRK
    Dyuratekuto α / MRK
    ガス硬化技術の「MRK」と、「デュラテクトα」を組み合わせた技術です。
    And "MRK" of gas curing technology, is a technology that combines the "Dyuratekuto α".
    硬質化した素材表面に硬質被膜が重なることで、更なる耐傷性を実現するほか、耐メタルアレルギー性も優れて います。
    By hard coating overlaps the hardening the surface of the material, in addition to achieve the further scratch resistance, also has excellent resistance to metal allergic.
    Hv2,200〜2,500
    Hv2,200~2,500
    「DURA(デュラ)」はラテン語で“硬い”の意味。
    The meaning of "DURA (Dura)" is a Latin word "hard".
    Hv ビッカース硬度:Vickers Hardness 材料の硬さを表す尺度。
    Hv Vickers hardness: measure of the hardness of Vickers Hardness material.
    表面硬化技術
    Surface hardening technique



    IP技術デュラテクトα デュラテクトPTIC デュラテクトTIC デュラテクトGOLD
    IP technology Dyuratekuto α Dyuratekuto PTIC Dyuratekuto TIC Dyuratekuto GOLD



    IP(イオンプレーティング)とは真空装置の中で金属をイオン化し、部品の表面に被膜をコーティングする技 術です。
    IP to ionize the metal in the (ion plating) and vacuum equipment, is a technology for coating a coating on the surface of the component.
    乾式めっきとも呼ばれ、腕時計には主に装飾目的で使用されてきました。
    Also referred to as dry plating, has been used mainly for decorative purposes is to watch.
    (③シチズンのイオンプレーティング P.58参照)
    (Ion see plating P.58 of ③ Citizen)
    シチズンでは独自の技術により硬質被膜のコーティング処理に成功。
    Citizen success in the coating process of the hard coating by unique technology.
    部品の材質、形状、仕上げにとらわれず適用範囲が広く、カラーバリエーションも豊富です。
    The material of the parts, shape, wide range of application agnostic to finish, color variation is also abundant.
    高級品、レディス、チタニウム、ステンレス商品と幅広いモデルに展開されています。
    Luxury goods, ladies, titanium, has been deployed in a stainless steel products and a wide range of models.

    低温プラズマ技術デュラテクトDLC
    Low-temperature plasma technology Dyuratekuto DLC



    プラズマCVD技術とは真空装置の中で原料物質を含むガスをプラズマ化し、化学反応させたのちに部品の表面 に吸着コーティングする技術です。
    Plasma The CVD technology into plasma gas that contains the raw material in a vacuum device, is a technology that adsorption coating to the surface of the component in the mixture was allowed to chemical reaction.
    DLC被膜はダイヤモンド構造を一部含んだC(炭素)とH(水素)からなるアモルファス構造をとり、結晶粒 界がないため高硬度で非常に滑らかな被膜です。
    DLC coating takes an amorphous structure consisting of containing a part of the diamond structure C (carbon) and H (hydrogen), is very smooth coated with a high hardness because there is no crystal grain boundaries.
    独特なダークグレー色は高級品、ファッションモデルのバリエーションのひとつとして拡大展開中 です。
    Unique dark gray color luxury goods, is expanding deployment as one of the variations of the fashion model.


    ガス硬化技術デュラテクトMRK
    Gas curing technology Dyuratekuto MRK



    真空炉にガスを封入し、熱処理を施すことでチタン素材の表面に20〜30μmの硬化層を形成させることによ り、時計の表面を硬質化する技術です。
    The gas sealed in a vacuum furnace, by forming a cured layer of 20~30μm on the surface of the titanium material by heat treatment, technology for hardening the surface of the watch.
    『軽い・錆びない・金属アレルギーを起こしにくい』というチタニウムの特性はそのままで、ケース表面の硬質 化に成功しました。
    Characteristics of titanium called "less prone to light not rust-metal allergy" as it is, has succeeded in hardening of the surface of the case.
    ハードな使用環境下で効果を発揮し、チタニウムのスポーツモデルに採用されています。
    To demonstrate the effect under hard use environment, it has been adopted in titanium sports model.

    複合硬質化技術デュラテクトDLC/MRK デュラテクトα/MRK
    Composite hard technology Dyuratekuto DLC / MRK Dyuratekuto α / MRK



    ガス硬化技術の「MRK」と、「デュラテクトα」または「DLC」を組み合わせた技術です。
    And "MRK" of gas curing technology, is a technology that combines the "Dyuratekuto α" or "DLC".
    硬質化した素材表面に硬質被膜が重なることで、更なる耐傷性を実現します。
    By hard coating overlaps the hardening the surface of the material, to achieve further scratch resistance.


    キズつきにくさの比較
    Comparison of flaws per difficulty



    当社キズ試験機による擦キズの比較
    Comparison of scratch friction by our scratch testing machine
    試験後のサンプル
    Sample after the test
    試験後表面の凹凸(粗さ)状況
    Unevenness of the test after the surface (roughness) situation

    TI(素材)
    TI (material)

    デュラテクトTIC
    Dyuratekuto TIC

    デュラテクトα
    Dyuratekuto α

    試験条件: アルミナ粉末(30μ)を1.5Kgfの加重にて30 回スライドさせたもの ※注意:硬いものに擦りつけたり、強い衝撃を加えるとキズや打痕がつく場合がありますのでご注意 ください。
    Test conditions: alumina powder (30μ) what was weighted at 30 times slide of 1.5Kgf ※ Note: Please note that hard or rubbed in things, because you might get is the addition of a strong shock scratches and dents.
    表面硬化処理ですので、素材そのものの硬化ではありません。
    Since it is a surface hardening treatment, not a cure of the material itself.
    材質硬度について
    About Material hardness



    代表的なケース(側)材質のビッカース硬度
    A typical case (side) Material of Vickers hardness

    ビッカース硬度(Hv)
    Vickers hardness (Hv)
    ビッカース硬度は、素材にダイヤモンド製の圧子を押し込むことで測定されます。
    Vickers hardness is measured by pushing the diamond of the indenter to the material.
    この試験方法は、極めて硬い材料も測定でき、また試験用途も大変広く、他の硬さ試験の基準にも利用されてい ます。
    This test method is also extremely hard material can be measured, also testing applications also very widely, has also been used on the standard of the other hardness test.
    表面被膜硬度については、低荷重で被膜硬度のみを測定したものです。
    For surface coating hardness, it is a measure of the only film hardness at low load.
    日常使用によるキズのつきにくさをそのまま表現する尺度ではありません。
    It is not a measure to directly express the luck difficulty of scratches caused by everyday use.
    耐摩耗性と美しい黒を実現するデュラテクトDLC
    Dyuratekuto DLC to achieve a beautiful black and wear resistance




    DLCとはDiamond Like Carbon(ダイヤモンドのようなカーボン)の略で、主に炭素と水素で構成される非晶質のカーボン硬質膜 のことです。
    The DLC stands for Diamond Like Carbon (carbon, such as diamond), is mainly that of amorphous carbon hard film composed of carbon and hydrogen.
    素材によって応用範囲が限定されていた表面加工技術DLCを独自の技術で改善。
    Improve the surface processing technology DLC the range of applications has been limited by the material in its own technology.
    従来難しかった素材への加工が可能となり、シチズン独自の<デュラテクトDLC>が高い耐摩耗性を持つ硬く 美しい黒のケースやバンドを実現します。
    It enables processing of the conventional was difficult material, providing a beautiful black case and band hard with the Citizen own <Dyuratekuto DLC> a high wear resistance.
    Last edited by CitizenPromaster; August 19th, 2016 at 13:27.

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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    Great post. I have been trying to figure this stuff out for a year.
    Quo Vadis?

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    Re: The definitive Citizen Titanium Thread / Super Titanium / Ti + IP / Duratect / MRK / DLC

    Good stuff. I am sure there is an online college somewhere willing to give you a BS/BA for this work.
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