Tous les titanes ne présentent pas les mêmes performances en milieu chimique. La nuance 2 résiste de manière fiable aux environnements oxydants tels que l'acide nitrique, mais elle ne résiste pas aux acides réducteurs tels que l'acide chlorhydrique et l'acide sulfurique à des concentrations supérieures à environ 5%. La nuance 7 — une nuance 2 enrichie en palladium — étend la résistance aux environnements acides réducteurs jusqu’à environ 10% d’HCl et environ 30% de H₂SO₄ à température ambiante. La nuance 12 (Ti-Mo-Ni) occupe une position intermédiaire : elle offre une meilleure résistance aux chlorures et aux saumures chaudes que la nuance 2, à un coût inférieur à celui de la nuance 7. La nuance 16, une variante à plus faible teneur en palladium de la nuance 7, offre des performances de résistance à la corrosion quasi équivalentes tout en permettant une réduction significative des coûts ; elle mérite donc davantage d’attention qu’elle n’en reçoit généralement. Ce guide met en correspondance chaque nuance avec des environnements acides spécifiques, en indiquant les seuils de concentration et de température sur lesquels les ingénieurs peuvent s’appuyer.
Pourquoi la décision relative aux notes a plus d'importance que vous ne le pensez
La résistance à la corrosion du titane provient d’un mince film passif de dioxyde de titane (TiO₂) capable de s’autoréparer, qui se forme spontanément en présence d’oxygène ou d’humidité. Dans les environnements oxydants — acide nitrique, acide chromique, la plupart des chlorures aqueux à température ambiante —, ce film est stable et se régénère rapidement s’il est endommagé. C’est pourquoi le titane non allié a fait ses preuves depuis 40 ans dans les condenseurs des usines d’acide nitrique.
Le problème réside dans les environnements réducteurs. Dans l’acide sulfurique chaud, l’acide chlorhydrique chaud ou tout autre environnement où l’oxygène dissous est épuisé (pH faible, température élevée, géométrie en interstice), ce film passif ne peut pas se maintenir. Le titane non allié commence alors à se corroder, parfois rapidement.
La stratégie d’alliage adoptée pour les nuances 7, 11, 16 et 17 répond directement à ce problème. Un faible ajout de palladium (0,05–0,25%) abaisse le potentiel de corrosion du titane à une valeur à laquelle le film passif reste stable, même dans des conditions réductrices et désaérées. Le mécanisme est électrochimique : le Pd agit comme un dépolariseur cathodique, déplaçant le potentiel de fonctionnement vers la zone de passivation. C’est pourquoi un ajout de 0,21 TP3T de Pd transforme le comportement de la nuance 2 dans l’HCl ou l’H₂SO₄ — il ne s’agit pas d’une simple modification mineure de la formulation, mais d’une réponse à la corrosion fondamentalement différente.
La classe 12 adopte une approche différente : l'ajout de molybdène et de nickel, qui améliore la stabilité du film passif dans les saumures chlorées chaudes, sans nécessiter de palladium, un métal coûteux.
Choisir une note inadaptée, que ce soit trop élevée ou trop basse, a un coût réel. Le fait de surdimensionner la nuance 7 pour une application impliquant de l'acide nitrique pur, alors que la nuance 2 convient parfaitement, multiplie par 2 à 3 le coût des matériaux sans apporter aucun avantage technique. Une sous-spécification de l'acier de nuance 2 dans un échangeur de chaleur 20% H₂SO₄ entraîne une défaillance due à la corrosion dans un délai de 12 à 18 mois. La décision n'est pas compliquée à prendre dès lors que l'environnement corrosif est correctement caractérisé.
Les cinq critères qui comptent vraiment dans le secteur des services chimiques
Plus de 95% de titane utilisé dans les procédés chimiques industriels se répartissent en cinq nuances. Les nuances 1, 3, 4 et 5 ont chacune leurs applications, mais les nuances 1 et 3 sont largement supplantées par la nuance 2 pour les applications chimiques ; la nuance 4 apporte une résistance mécanique accrue sans offrir d’avantage en matière de résistance à la corrosion ; et la nuance 5 (Ti-6Al-4V) est un alliage utilisé dans l’aérospatiale qui présente en réalité pire une meilleure résistance à la corrosion que les nuances CP dans la plupart des milieux chimiques.
| Grade | Désignation | Composition | Niveau de coût | Utilisation principale du produit chimique |
|---|---|---|---|---|
| Niveau 2 | CP-Ti, ASTM R50400 | 99%+ Ti | Valeur de référence | Acides oxydants, acide nitrique, acides réducteurs dilués à température ambiante |
| 7e année | Ti-0,2Pd, ASTM R52400 | Grade 2 + 0,12–0,251 TP3T Pd | 2 à 3 fois le niveau 2 | Acides réducteurs : HCl, H₂SO₄, acide phosphorique, acides organiques |
| 11e année | Ti-0,2Pd, ASTM R52250 | Catégorie 1 + 0,12–0,251 TP3T Pd | Similaire à la 7e | Identique à la nuance 7, mais avec une meilleure formabilité (pièces à parois minces) |
| 12e année | Ti-Mo-Ni, ASTM R53400 | Ti + 0,3% Mo + 0,8% Ni | ~1,3 à 1,5 fois le niveau 2 | Saumures chaudes riches en chlorure, eau de mer, milieux acides mixtes |
| 16e année | Ti-0,05Pd, ASTM R52402 | Catégorie 2 + 0,04–0,081 TP3T Pd | ~1,5 à 2 fois le niveau 2 | Niveau quasi équivalent à celui de la 7e, pour un coût en Pd inférieur |
Normes applicables aux formes de produits : tôles/bandes/plaques (ASTM B265), tubes sans soudure et soudés destinés à des applications en milieu corrosif (ASTM B337), tubes soudés pour échangeurs de chaleur (ASTM B338), tubes sans soudure (ASTM B861), tubes soudés (ASTM B862), pièces forgées (ASTM B381).
Niveau 2 — Référence pour les milieux acides oxydants
La nuance 2 est le choix par défaut approprié pour les applications en milieu acide oxydant ; ce n'est toutefois pas le bon choix en présence de conditions réductrices.
Dans la pratique, les élèves de CE1 obtiennent d'excellents résultats dans les domaines suivants :
- Acide nitrique (HNO₃) : Résistant à toute la gamme des concentrations couramment rencontrées dans l'industrie (10–65%) et à des températures allant jusqu'au point d'ébullition. Ses performances sont supérieures à celles de la plupart des alliages de nickel dans les flux d'acide nitrique contaminés contenant des fluorures, qui accélèrent la corrosion des aciers inoxydables mais pas celle du titane.
- Acide chromique : Résistant à toutes les concentrations à température ambiante.
- Chlore liquide et hypochlorite : Stable jusqu'à 2% de Cl₂ dans les conditions ambiantes — largement utilisé dans les usines de chlore et de soude pour les anodes, les canalisations et les équipements de manutention.
- Acide sulfurique et acide chlorhydrique dilués à température ambiante : La classe 2 tolère les acides réducteurs dilués à condition que la température soit basse et qu'il y ait de l'oxygène dissous. Limites pratiques : H₂SO₄ jusqu'à environ 5% à 25 °C, HCl jusqu'à environ 1–2% à 25 °C en présence d'oxygène dissous.
Les lacunes de la classe de CE1 :
- Concentration en H₂SO₄ supérieure à 5% ou température supérieure à 60 °C
- HCl au-dessus d'environ 5–71 TP3T à température ambiante dans des conditions d'aération, ou au-dessus d'environ 1–21 TP3T à des températures élevées ou en cas de manque d'oxygène
- Acide phosphorique chaud à plus de 60 °C et dont la concentration est supérieure à 10%
- Any crevice geometry in hot chloride solutions above 80°C
The 80°C crevice corrosion threshold is important for equipment design. In heat exchanger tube-to-tubesheet joints, flange face contact areas, or gasketed connections, crevice geometries are unavoidable. At temperatures above 80°C in chloride media, Grade 2 can experience localized crevice attack even in environments where it shows no general corrosion.
Grade 7 — The Premier Choice for Reducing Acid Environments
Grade 7 is the most corrosion-resistant commercially available titanium alloy, and the correct specification when reducing acids, elevated temperatures, or crevice risk are present.
The palladium content (0.12–0.25% by weight) shifts titanium’s corrosion potential by approximately +200 mV vs the unalloyed material. This shift is enough to place the operating potential within the passive region in deaerated, reducing acid environments where Grade 2 would be active and corroding.
Practical performance data:
- Hydrochloric acid (HCl): Grade 7 resists corrosion up to approximately 20–27% concentration at 25°C (iso-corrosion curves from TIMET mill data). Grade 2 in aerated HCl handles up to ~5–7% at room temperature, but that limit drops sharply at elevated temperatures or when dissolved oxygen is depleted.
- Sulfuric acid (H₂SO₄): Resistant up to ~45% at 25°C, ~20% at 60°C, ~7% at boiling. Unalloyed Grade 2 begins to corrode above ~5% at room temperature.
- Phosphoric acid (H₃PO₄): Grade 7 handles concentrations up to ~80% at room temperature; Grade 2 is limited to ~30% at 25°C, and significantly less at elevated temperatures.
- Organic acids (acetic, formic, oxalic): Grade 7 is essentially inert across the full range of commercial concentrations at temperatures up to 100°C.
- Crevice corrosion threshold: Grade 7 does not suffer crevice corrosion in chloride solutions at temperatures below 250°C (at pH above 1). Grade 2’s threshold is 80°C. This difference alone justifies Grade 7 for hot brine heat exchangers where crevice geometry cannot be eliminated.
Grade 7 also offers resistance to wet HCl gas and mixed acid systems common in pharmaceutical manufacturing — environments where neither stainless steel nor nickel alloys perform adequately without cost-prohibitive alloy selection.
The two environments where Grade 7 still fails:
- Hydrofluoric acid (HF): All titanium grades are attacked by HF. The fluoride ion dissolves the TiO₂ passive film. No titanium grade is suitable for HF service — use zirconium, PTFE-lined equipment, or Hastelloy C-276.
- Fuming nitric acid (red fuming HNO₃ with >5% NO₂): Can cause stress corrosion cracking in titanium. This is a specific exception to titanium’s generally outstanding nitric acid resistance.
Grade 12 — The Cost-Efficient Workhorse for Chloride and Hot Brine Service
Grade 12’s molybdenum and nickel additions give it resistance in hot chloride environments that Grade 2 can’t match — at roughly half the premium of Grade 7.
Grade 12 (Ti-0.3Mo-0.8Ni) doesn’t use palladium, which eliminates the largest cost driver in Grade 7 pricing. Instead, Mo and Ni stabilize the passive film specifically in hot brine, seawater, and mixed chloride-acid environments.
Compared to Grade 2:
- Crevice corrosion resistance in seawater extends to approximately 120°C (vs. 80°C for Grade 2)
- Better resistance to hot phosphoric acid containing halide impurities
- Improved tensile strength (approximately 483 MPa minimum vs. 345 MPa minimum for Grade 2) — allows thinner wall construction
- Better resistance in hot sodium hypochlorite solutions
Compared to Grade 7:
- Grade 12 is generally inferior in straight reducing acid service (HCl, H₂SO₄)
- Grade 12 performs comparably or better in hot chloride brines and seawater systems where the primary concern is crevice attack, not reducing acid corrosion
- Grade 12 has no advantage in HF environments (both fail)
Best-fit scenarios for Grade 12:
- Offshore desalination and produced water handling (hot saline, elevated temperature)
- Pulp and paper bleach plant equipment exposed to chloride/hypochlorite mixtures
- Marine chemical processing where seawater cooling is combined with mild acid exposure
- Refineries with brine recirculation systems where straight acid resistance isn’t needed
Grade 16 — The Underdiscussed Alternative to Grade 7
Grade 16 contains roughly half the palladium of Grade 7 (0.04–0.08% vs. 0.12–0.25%) and delivers corrosion resistance that is, in most practical chemical environments, indistinguishable from Grade 7.
This grade receives almost no attention in standard engineering guidance despite a straightforward value proposition: palladium consistently accounts for a significant fraction of the cost premium in Grade 7 and Grade 11 plate and tubing. At Pd market prices, a plate order in Grade 16 can cost 20–35% less than an equivalent Grade 7 order with comparable corrosion performance in the majority of process environments.
The corrosion mechanism is the same — Pd addition shifts the corrosion potential into the passive region — and test data from TIMET and the Corrosion Engineering literature shows that 0.05% Pd is sufficient to achieve passive behavior in most reducing acid environments. The advantage of higher Pd content (Grade 7) appears primarily at the extremes: very concentrated reducing acids, very high temperatures, or environments where the corrosion potential is driven particularly low.
When to specify Grade 16 over Grade 7:
- Service environments within the moderate range (H₂SO₄ <20%, HCl <5%, temperatures below 80°C)
- Applications where cost pressure is significant and the engineer can document equivalency from published test data
- Projects requiring large plate quantities where the cost delta is material (fabrication of reactor shells, large heat exchanger shells)
When to stick with Grade 7:
- Hot concentrated reducing acid service near the upper limits of Grade 7’s corrosion resistance
- Applications where conservative specification is contractually required (nuclear, pharmaceutical process equipment with FDA validation)
- Crevice environments above 200°C — the higher Pd content provides more conservatism
Grade 17 is the Grade 1-based equivalent of Grade 16 (more ductile, lower strength) and follows the same logic for applications requiring extreme formability with reducing acid resistance.
Acid-by-Acid Selection Framework
The most direct way to use this information is an acid-environment matrix. The table below reflects commonly referenced data from TIMET corrosion manuals and published corrosion engineering literature.
Titanium Grade Selection by Acid Environment
| Acide | Concentration | Température | Niveau recommandé | Notes |
|---|---|---|---|---|
| Nitric acid (HNO₃) | 10–65% | Up to boiling | Niveau 2 | All CP grades adequate; Grade 7 offers no advantage |
| Nitric acid (red fuming) | >5% NO₂ | Any | Avoid all Ti | SCC risk in all grades |
| Sulfuric acid (H₂SO₄) | <5% | <60°C | Niveau 2 | Dissolved O₂ must be present |
| Sulfuric acid | 5–45% | <60°C | Grade 7 or Grade 16 | Grade 2 corrodes above 5% |
| Sulfuric acid | >45% | Any | Grade 7 (with caution) | Test data required; consider Zr or Ta above 60% |
| Hydrochloric acid (HCl) | <5–7%, aerated | RT only | Niveau 2 | Dissolved O₂ required; limit drops sharply at elevated T |
| Hydrochloric acid | 5–27% | Up to 50°C | Grade 7 or Grade 16 | Grade 2 not adequate above ~5–7% aerated |
| Hydrochloric acid | >27% | Any | Consult test data | Grade 7 may corrode above 27% at elevated T |
| Phosphoric acid (H₃PO₄) | <30% | <80°C | Niveau 2 | Acceptable with aeration |
| Phosphoric acid | 30–80% | Any | Grade 7 or Grade 16 | Grade 12 acceptable if halide-free |
| Hydrofluoric acid (HF) | Any | Any | Aucun | All Ti grades fail — use Zr, PTFE-lined, or Hastelloy |
| Organic acids (acetic, formic) | All commercial | <100°C | Grade 2 or Grade 7 | Grade 2 in dilute, Grade 7 for concentrated/hot |
| Hot chloride brine | NaCl >10%, >80°C | 80–150°C | Grade 12 or Grade 7 | Grade 2 crevice risk above 80°C |
| Hot hypochlorite | NaOCl >1%, >60°C | Up to boiling | Grade 12 or Grade 7 | Grade 2 marginal above 60°C |
| Wet Cl₂ gas | Up to 2% | <100°C | Niveau 2 | All CP grades adequate in wet Cl₂ |
This framework covers the most common acid environments in chemical processing. Mixed acid systems, contaminated streams (e.g., HNO₃ + HF in stainless steel pickling), and proprietary process fluids require individual corrosion testing — no published table fully substitutes for immersion testing in the actual process fluid.
The Palladium Premium: When Grade 7 Cost Is Hard to Justify
Palladium trades at roughly $1,000–$1,500 per troy ounce. Grade 7 contains 0.12–0.25% Pd by weight — in a 1,000 lb plate order, that’s approximately 1.2–2.5 lbs of palladium embedded in the alloy. That Pd content adds a material premium that is directly tied to palladium spot pricing.
When a Grade 2 plate runs $5–8/lb and Grade 7 runs $12–18/lb, the cost decision deserves engineering rigor rather than defaulting to the higher grade out of caution.
A simple ROI framing:
- Cost of premature Grade 2 failure: Unplanned shutdown to replace a heat exchanger in a continuous-process chemical plant can cost $200,000–$500,000 in lost production, plus $50,000–$150,000 in replacement materials and labor.
- Cost of upgrading to Grade 7: On a 10,000 lb heat exchanger bundle, the Grade 7 premium over Grade 2 might be $70,000–$100,000.
- Break-even: If Grade 7 extends service life by even 2–3 years in a reducing acid environment where Grade 2 would fail in 1–2 years, the economics strongly favor Grade 7.
Grade 16 changes this math further. If Grade 16 pricing comes in at $8–12/lb — which reflects the lower Pd content — and it delivers equivalent service life in that specific environment, the premium over Grade 2 drops to a range where even modest reliability improvement justifies the upgrade.
The practical recommendation: default to Grade 2 for verified oxidizing-only environments, Grade 16 for moderate reducing acid service where cost matters, and Grade 7 for aggressive reducing acid environments or where crevice corrosion at elevated temperature is a known risk.
Fabrication and Welding: Where Grade Selection Gets Invalidated
Titanium’s corrosion resistance can be destroyed by poor welding practice regardless of grade specified. This point is underemphasized in most grade selection guides.
The critical issue: alpha-case formation. When titanium is welded or heated above 600°C in the presence of air, nitrogen, or oxygen, a hard, brittle, oxygen-rich surface layer called alpha-case forms. Alpha-case has poor ductility and, critically, degraded corrosion resistance because its chemistry no longer matches the base alloy.
For chemical service welding:
- Inert gas shielding is mandatory — on both weld face and weld root. Back-purging with argon (minimum 99.995% purity) is not optional in titanium welding for chemical service. A “color check” of the weld bead is the practical quality indicator: silver-white is acceptable, straw-yellow is borderline acceptable, blue or purple means oxygen contamination and the weld must be rejected.
- Titanium must be welded with titanium filler wire of the same or lower grade. Do not use Grade 5 filler (Ti-6Al-4V) for Grade 2 or Grade 7 base metal — the filler’s aluminum content degrades corrosion resistance in the weld zone.
- Surface cleanliness: Titanium reacts with iron at weld temperatures. Iron contamination from grinding with steel tools, contact with steel wire brushes, or iron particles in the shop environment can cause localized corrosion at welds. Dedicated stainless steel brushes and clean work areas are required.
- Post-weld passivation: Titanium typically doesn’t require chemical passivation (unlike stainless steel), but mechanical removal of any discolored weld zones followed by solvent cleaning is good practice before placing equipment into service.
Grade 7 and Grade 12 weld in essentially the same way as Grade 2 — no special parameters beyond the standard titanium welding requirements above. The corrosion resistance at welds matches the base metal when done correctly.
Summary: Matching Grade to Environment
Titanium grade selection for chemical processing reduces to a small number of decisions:
Is the acid environment primarily oxidizing? → Grade 2 is the standard specification. It delivers 40+ year service life in nitric acid, chromic acid, and wet chlorine service at a competitive cost.
Are reducing acids present (HCl, H₂SO₄, hot phosphoric)? → Specify Grade 7 or Grade 16. The palladium addition is not a luxury in these environments — it is what makes titanium viable at all. Grade 16 is the cost-conscious choice for service within moderate concentration and temperature limits.
Is hot chloride brine or seawater the primary concern, not reducing acids? → Grade 12 is the fit. The Mo-Ni addition addresses the specific crevice corrosion mechanism in hot saline environments at a lower cost than Pd-bearing grades.
Is hydrofluoric acid involved? → No titanium grade works. Stop the evaluation and consider zirconium, PTFE-lined construction, or Hastelloy C-276.
The grade selection itself is only half the engineering decision. Weld quality, joint design to minimize crevice geometry, and process stream characterization (particularly dissolved oxygen content, temperature profile, and contaminant ions) determine whether the specified grade performs as intended. A correctly specified Grade 2 with clean welds in a nitric acid environment will outlast poorly fabricated Grade 7 in the same environment every time.
Questions fréquemment posées
What is the most corrosion-resistant titanium grade for chemical service?
Grade 7 (Ti-0.2Pd) is the most corrosion-resistant commercially available titanium alloy. Its palladium addition shifts the corrosion potential into the passive region in reducing acid environments where unalloyed titanium corrodes. It resists HCl up to ~10% and H₂SO₄ up to ~30% at ambient temperature, and does not suffer crevice corrosion in chloride solutions below 250°C at pH above 1.
When should I use Grade 12 instead of Grade 7?
Grade 12 is the preferred choice when the primary corrosion risk is hot chloride brine or seawater exposure — not reducing acids. Its Mo-Ni addition provides superior crevice corrosion resistance in hot saline environments compared to Grade 2, at lower cost than Grade 7. If your process involves hot H₂SO₄ or HCl, Grade 7 outperforms Grade 12.
What is the difference between Grade 7 and Grade 16?
Both grades use palladium additions to improve reducing acid corrosion resistance. Grade 7 contains 0.12–0.25% Pd; Grade 16 contains 0.04–0.08% Pd. Grade 16’s lower Pd content makes it less expensive, and in most practical chemical processing environments within moderate acid concentrations and temperatures, its corrosion performance is equivalent to Grade 7. Grade 7 provides more conservatism at extreme conditions.
Does titanium corrode in hydrofluoric acid?
Yes. All titanium grades are attacked by hydrofluoric acid (HF) and fluoride-containing solutions at pH below approximately 3. Fluoride ions dissolve the protective TiO₂ passive film. No titanium grade should be specified for HF service — use zirconium, fluoropolymer (PTFE/PFA) lined equipment, or nickel alloys such as Hastelloy C-276.
Is Grade 2 titanium acceptable for sulfuric acid service?
Grade 2 is acceptable for dilute sulfuric acid (less than 5% H₂SO₄) at ambient temperature when dissolved oxygen is present. Above 5% concentration, above 60°C, or in deaerated conditions, Grade 2 corrodes at unacceptable rates. Grade 7 or Grade 16 should be specified for any H₂SO₄ service above these thresholds.
Why does weld quality matter so much in titanium chemical equipment?
Titanium welded without adequate inert gas back-purging develops an oxygen-contaminated surface layer (alpha-case) that has degraded corrosion resistance and poor ductility. A visually perfect weld with blue or purple discoloration is a failed weld in chemical service. Titanium welding requires argon back-purging, dedicated tools free of iron contamination, and weld color inspection as a mandatory quality check.
